i hereby declare that the work contained in this thesis
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I hereby declare that the work contained in this thesis was carried out by myself during the period 1993-1996. The work contained in this thesis has not been submitted for any other degree or diploma.
ACKNOWLEDGEMENTS
I would like to thank Professor Brian Johnson for his unbridled enthusiasm and knowledge of the material contained in this work. Special thanks to Dr Philip Bailey for taking over my supervision in the final year, and for his excellent proof reading of this thesis. Thanks to Zeneca in Grangemouth, particularly Dr Nick Evens, for their financial support. Thanks also to Dr Simon Parsons for the crystallographic work contained in this thesis.
Thanks to the many people I have shared a lab with over the years: Ruth M., Ali, Scott, Jane, Gideon, Ruth P., Ken, Nick, and Alan, and also to the many other people in the group, and at Edinburgh, who made my time there so enjoyable. Thanks also to the technicians responsible for all the NMR and mass spectroscopy data included in this thesis.
Special thanks to my parents without whom this thesis would not have been possible. And finally to Lesley, for all her support and love over the years.
List Of Compounds And Numbers
1 { (bpy)Pd(C6H1000CH3)) (OTf) 2 { (bpy)Pd(C6H8COCH3) } (OTf) 3 { (bpy)Pd(C6H8COCH3) ) (OTf) 4 { (bpy)Pd(C6H 12COCH3) } (OTf) 5 { (bpy)Pd(C6H6COCH3) } (OTI) 6 {(bpy)Pd(C 6H5FCOCH3)}(OTf) 7 {(bpy)Pd(C 6H5BrCOCH3) } (OTt) 8 {(bpy)Pd(C 8H8COCH3)} (OTt) 9 { (bpy)Pd(C6H5CH3COCH3) } (OTt) 10 { (bpy)Pd(C 6H4(OH)2COCH3) } (OTt) 11 (tmeda)Pd(Ph) 2 12 0s3(CO)12 13 0s3(CO) io(MeCN)2' 14 0s3(C0)9(p.-H)2(C6H3F) 15 Os3(C0)9(t-H)2(C6H3C1) 16 0s3(C0)io(.i-Br)2 17 0s3(C0)9(t-H)2(C6H3CH3) 18 0s3(CO)9Q.x-H)2 {ortho-C6H2(CH3)3 } 19 Os3(CO)9(t-H)2 {meta-C 6H2(CH3)2 } 20 Os3(CO)9(j.t-H)2 {para-C 6H2(CH3)2) 21 0s3(C0)9(p-H)2 { C 6H3C(CH3)CH2) } 22 0s3 (C0)9Q.-H)2 { C6H3C(CH3)CH2) } 23 0s3(C0)9(j.t-H)2(C6H3CHCH2) 24 0s3(C0)9Qt-H)2 { C6H2(C(CH3)CH2)2) 25 Os3 (C0)9(t-H)2{ C 6H3F(COMe) } 26 Os3(C0)9(t-H)2 { C 6H3C1(COMe) } 27 0s3(CO)9(t-H)2 { C6H3CH3(COMe)) 28 0s3(CO)9(p-H)2 { ortho-C6H(CH3)2(COMe)) 29 0s3(CO)9Q.t-H)2 {meta-C 6H(CH3)2(COMC) } 30 Os3 (CO)8(.t-H)(CH2CHCHCH3)(C6H3F) 31 0s3(CO)8(p.-H)2(CH3HCCH3)(C6H3F)
Contents
1 CHAPTER ONE- INTRODUCTION
1 1 Friedel-Crafts Reactions
1 1.1 Introduction
2 1.2 Historical
4 1.3 Aromatic Ketone Synthesis
4 1.3.1 Introduction
5 1.3.2 Mechanism
6 1.3.3 Ratios and Addition Sequences
7 1.3.4 Solvents
8 1.3.5 Catalysts
15 1.3.6 Acyl Component
19 1.3.7 Houben-Hoesch Reaction
21 1.3.8 Fries Rearrangement
23 1.4 Conclusion
24 2 Cluster Chemistry
24 2.1 Introduction
24 2.2 The Surface Cluster Analogy
28 2.2.1 Chemisorption of Ethylene on a Pt(1 11) Surface
29 2.2.2 CO-adsorption of Benzene and CO on Rh(1 11)
31 2.3 Trinuclear Cluster Arene Chemistry
31 2.3.1 Introduction
32 2.3.2 Structures and Bonding Modes
33 2.3.3 Synthesis
37 2.3.4 Reactions
40 2.3.5 Conclusion
41 3 References
49 CHAPTER TWO- PALLADIUM COMPLEXES AS ACYLATION
CATALYSTS.
49 2.1 Introduction
49 2.1.1 Palladium Complexes and their use in Synthesising
CO/alkene Co-Polymers
56 2.1.2 Industrial Background
60 2.2 Reactions of(bpy)Pd(COMe)(I) with Cyclic Alkenes and Diene
62 2.3 Reactions of(bpy)Pd(COMe(I) with Arenes
64 2.4 Reaction of(tmeda)PdC1 2 with Phenyl Lithium
67 2.5 Conclusion
68 2.6 References
69 CHAPTER THREE- SYNTHESIS OF ARYNE OSMIUM CLUSTERS
69 3.1 Introduction
74 3.2 Reactions of 0s3(C0) 10(MeCN)2
74 3.2.1 Reactions of 0s3 (CO) io(MeCN)2 with Arenes of the Type
C6115R (where R = F, Cl, Br, and CH 3)
82 3.2.2 Reactions of 0s 3(CO) 1o(MeCN)2 with C6H4(CH3)2
87 3.2.3 Conclusion
89 3.3 Reactions of 0s 3(C0) 10(MeCN)2 with a-methylstyrene, styrene,
and 1,3 diisopropenylbenzene
89 3.3.1 Results and Discussion for Reaction with a-
methyistyrene
91 3.3.2 Results and Discussion for Reaction with styrene
92 3.3.3 Results and Discussion for Reaction with 1,3
diisopropenylbenzene
92 3.3.4 Conclusion
94 3.4 References
95 CHAPTER FOUR- REACTIONS OF OSMIUM ARYNE CLUSTERS
95 4.1 Introduction
95 4. 1.1 Attack on Metal Framework
98 4.1.2 Attack on the Arene Ring
100 4.2 Reactions of Clusters 0s 3(C0)9(t-H)2(C6H2R'R2) Towards
Acylation
105 4.3 Reaction of 0s3(C0)9(.t-H)2(C6H3F) with 2-butyne
114 4.4 References
115 CHAPTER FIVE- EXPERIMENTAL
115 5.1 General Experimental Procedures and Instrumentation
118 5.2 Experimental Details for Chapter Two
124 5.3 Experimental Details for Chapter Three
131 5.4 Experimental Details for Chapter Four
135 5.5 References
136 5.6 Crystallographic Tables
Chapter One
Chapter One
INTRODUCTION
The introduction which follows in this chapter is divided into two distinct
sections, Friedel-Crafts Acylation Reactions and Cluster Chemistry. This is to reflect,
and give a background to, the later work contained in this thesis.
In the first section the introduction deals with Friedel-Crafts Acylation
Reactions, and covers in detail the different aspects and areas of Friedel-Crafts
Aromatic Ketone Synthesis. This is to give a background to the work carried out in
Chapter 2, which is concerned with using Palladium complexes as acylation catalysts.
In the second section the introduction deals with Cluster Chemistry, covering
in detail the Surface Cluster Analogy, and the synthesis, reactions, and bonding modes
in Trinuclear Arene Cluster Chemistry. This is to give an understanding of this type of
chemistry in relation to the cluster work carried out in Chapters 4 and 5.
1 FRIEDEL-CRAFTS REACTIONS
1.1 Introduction
Friedel-Crafts reactions are named after the two men who first discovered and
observed the action of aluminium chloride in organic reactions, Charles Friedel and
James Mason Crafts. Fnedel-Crafts reactions, as they are now termed, have grown
with the Grignard methods to be the most widely used, and versatile tools of organic
chemistry, covering aromatic and aliphatic systems alike.
1
Chapter One
1.2 Historical
Before Friedel and Crafts first publication (l) earlier workers had reported
reactions similar in character. In 1869 Zincke 2 reported the formation of
diphenylmethane during the attempted synthesis of 3-phenylpropionic acid. The
reaction was carried out in a benzene solution in the presence of Cu or Ag to remove
the metal chloride which is formed with the chlorine gas. However he noted the
evolution of HCl gas and the formation of diphenylmethane.
CHC1 CH2CH2COOH
+ CICH2COOH + C12
CH2C1
II I + AgorCu IN
+ HCI
Scheme 1.2.1: synthesis of 3-pheny1propiomc acid and diphenylmethane
In Zincke's later work ' 2 , he investigated the similar reactions of toluene,
benzene, and xylene. In these reactions he discovered that Zn powder enabled the
reaction to proceed more easily. Later papers (4,5) re-emphasised the use of Zn or
reduced Fe.
The first mention of acylation related to the latter Friedel-Crafts method
appeared in a communication by Grucarevic and Merz, 6 and was closely followed by
a paper by Zincke. 7 In Zincke's paper he attempted to synthesise dibenzoyl from
benzoyl chloride, in the presence of Cu, Zn, or Ag. Instead he noted evolution of HCl
gas and the formation of benzophenone. He also reported similar reactions with
toluene and xylene.
napier tjne
0 II
O(coc1 a + + I II.I
Scheme 1.2.2: Reaction between benzoyl chloride and benzene at room temperature
Grucarevic and Merz in their main communication 8 confirmed Zincke's work
and they then extended it to more aromatic compounds.
None of these papers realised that it was the metal chloride that catalysed the
reaction although some had observed its formation. It was left to Friedel and Crafts to
prove and demonstrate that it was the metal chloride that was the catalyst. Their first
two communications (9,10) gave details of the action of aluminium chloride on amyl
chloride to produce hydrocarbons and HC1 gas. They realised that the residues were
longer chain hydrocarbons that had been produced by combining the shorter chain
hydrocarbons in the reaction.
They then extended this work to attempt to create a general synthesis suitable
for use with any hydrocarbons, and they succeeded in synthesising amyl benzene(ii)
from amyl chloride, benzene and aluminium chloride.
II I + CH3(CH2)4C1
0((CH2)4CH3 +
Scheme 1.2.3: Reaction between benzene and amyl chloride in the presence of Aid 3
In a further paper " 2 they described the synthesis of diphenylmethane,
triphenylmethane, acetophenone, benzophenone, phthalophenone, and anthraquinone.
The paper attempted to show the generality of their method and to work out some of
the reaction's limitations.
C]
Chapter One
In later years "2 ' 7 they extended the scope of their reaction to include the use
of organic bromides and iodides, and to use aluminium bromide and aluminium iodide
to give alkylated and acylated products. They also extended their work into the use of
other metal halides, zinc chloride and ferric chloride, and they proved that the earlier
work by Zincke and others was due to the presence of zinc chloride acting as a
catalyst in the reaction.
1.3 Aromatic Ketone Synthesis
1.3.1 Introduction
The essential reaction of Friedel-Crafts ketone synthesis is between an acyl
component and an aromatic substrate in the presence of a catalyst to give an aromatic
ketone. A typical reaction is shown below in Scheme 1.3.1.1.
RCOC1 + ArH Aid3
" ArCOR + HO
Scheme 1.3.1.1: General equation for the reaction of an acyl chloride with an aromatic substrate
A variety of acyl groups can be used, and are usually acids, anhydrides or
esters.
Aid 3 ArH ± RCOX ArCOR + HX
ArH + (RCO)20 A103
b. ArCOR + RCOOH
ArH + RCOOH' BF3 ArCOR + H20
Aid 3 ArH + RCOOR' ArCOR + R'OH
Scheme 1.3.1.2: General reactions of acyl halides, anhydrides, carboxylic acids, and esters with an
aromatic substrate
4
Chapter One
1.3.2 Mechanism
The mechanism for the acylation reaction can proceed in one of two ways;
O—MX3 I O—MX3
R— + AsH I R—C—X I I + X [ ArH
Path I I 0+ MX' O—MX3 O—MX3
R—C R—C __ 4 R—C
x Ar Ar
+ IIX
OtMX3
R—C - - MX,- + RCO
Path B 0+ UX - 3
RCOArH MX4
R—C' Ar
'I
Scheme 1.3.2.1: Reaction mechanisms for aromatic ketone synthesis
Path A involves a reagent which may or may not be solvated. Gore (18) showed
that Path A is always the more likely mechanism, unless there are steric
considerations in the acyl halide or aromatic substrate.
Path B is an acylium cation mechanism (19) and is the more likely mechanism
when sterically bulky reagents are used, and when the substitution position on the
aromatic is sterically hindered. The structure of the acylium cation intermediate was
first proposed by Meerwein, 20 and results of exchange studies (21) have suggested the
Chapter One
presence of acylium cations in solution. In these experiments halogen exchange was
observed between aluminium halides and 2,4,6-tribromobenzoyl halides. It is argued
that the steric hindrance of this aromatic group precludes the formation of any other
intermediate except the acylium cation.
1.3.3 Ratios and Addition Sequences
In practice the use of the catalyst in the stoichiometric amount gives the
maximum total yield of ketone. A deficiency of catalyst will lower the overall yield
because of incomplete use of the acyl compound. Insufficient use of aluminium
chloride may cause self-condensation of the partially complexed ketone, as in the
formation of dypnone in the attempted acylation of benzene. (22)
The stoichiometric equations 123-291 for the formation of the reactive complex
with aluminium chloride are shown below in Scheme 1.3.3.1.
RCOC1 + Aid 3 P, RCOCIAIC13 (1)
RCOOH + 2A1C13 o RCOCIA1C13 + A100 + HCl (2)
RCOOR' + 3A1C13 ip RCOCLAICI3 + AI00 + R'Cl (3)
(RCO)20 + 3A1C13 01 2RCOCLA1C13 + A100 (4)
Scheme 1.3.3.1: Stoichiometric equations for the formation of the reactive complex
In practice the ratio of moles of aluminium chloride:acyl component of 1.1:1
has been found to be optimum for equation 1,(25) at least 2:1 for equation 2.2:1
for equation 3,(31) and at least 3:1 for equation 4(32) Similar ratios have been found
for other catalysts, and experimental values found to be in close agreement with those
calculated.
Chapter One
Gradual addition of one component to a mixture of the other two, usually in a
solvent, provides the three general experimental methods used in Friedel-Crafts
ketone synthesis.
Elbs Procedure
This is the most widely used procedure, and is the one which Friedel and
Crafts used themselves. It was further developed by Elbs, 33 and in this method the
catalyst is added last to the acyl chloride/aromatic mixture.
Bouveault Procedure
In this method the acyl halide is added last to the catalyst/aromatic mixture. (34)
This procedure is generally not preferred as the presence of hydrogen halide, formed
after the first addition of acyl halide, or from impurities, can cause extensive
isomerisation or disproportionation.
Perrier Procedure
In the Perrier method (31,11) of the reaction the aromatic substrate is added last
to the catalyst/acyl halide mixture. The reaction is generally carried out in carbon
disulfide, dichloromethane, or ethylene chloride as the solvent, because the complex
RCOC1.A1CI 3 is soluble in these solvents, but aluminium chloride is not. This means
that excess aluminium chloride will not be used in the reaction. When the aromatic
substrate has been added, the acylation product tends to be insoluble and is therefore
difficult to purify.
1.3.4 Solvents
A variety of solvents can be used in Friedel-Crafts ketone synthesis.
Nitrobenzene and carbon disulfide are the most commonly used, and these at the same
time govern the type of the reaction taking place. A polar solvent, such as
nitrobenzene, not only dissolves aluminium chloride but also the RCOC1.A1C1 3
7
Chapter One
complex and the aluminium chloride complex of the ketone. (17) This makes the
reaction essentially homogeneous in nature.
In a non-polar solvent, such as carbon disulfide, neither the aluminium chloride
or the complex RCOC1.A1C13, are appreciably soluble, making the reaction
heterogeneous in nature. In an intermediate solvent, such as dichloromethane,
aluminium chloride is not appreciably soluble, (3 ') but the complex RCOC1.A1C1 3 is.
The main factors governing solvent choice have been discussed by Gore (39) and
the main influence is the yield of the ketone obtained in the reaction. The choice of
solvent can affect the acylation rate observed for the reaction, as in the case of the
benzoylation of toluene. (40) The relative rates varied form 1.0 in 1,2,4-
trichlorobenzene, to 30 in excess benzoyl chloride.
Minor differences in the orientation of substitution have been observed with
benzene derivatives. For example in the case of the benzoylation of chlorobenzene,
twice as much meta-isomer is formed in nitrobenzene as in using excess
chlorobenzene. 41
1.3.5 Catalysts
1.3.5.1 Aluminium Chloride
Aluminium chloride is the main catalyst used in Friedel-Crafts reactions,
mainly because of its high catalytic activity and relative cheapness.
The purity of the aluminium chloride may have some influence on the yield of
the product, 42 as in the case of the benzoylation of benzene where the use of pure
aluminium chloride (99.95%) gave a higher yield than commercial aluminium chloride
(98%). Trace amounts of ferric chloride have been reported to cause increases in
Ll
Chapter One
yields (43) and to exert an accelerating effect on the reaction (44) when used in
conjunction with aluminium chloride.
Traces of water have been used to moderate otherwise violent reactions, (45)
and alternatively to accelerate sluggish reactions. 46 In other investigations 47 '48 it has
been observed that a little water added to the anhydrous aluminium chloride causes
considerable improvements in yield. In general practice perfectly anhydrous conditions
are difficult to obtain, and the activating influence of water has been explained (49) by
the formation of hydrates of the type [A1X 30H] H , which probably function like
other strong proton acids.
The use of partially hydrated or pure anhydrous aluminium chloride can result
in different products being formed, as in the case of the reaction of trichloroacetyl
chloride and benzene. If moist aluminium chloride is used the product observed is
trich1oroacetophenone, 50 but with anhydrous aluminium chloride the product is
triphenylvinyl alcohol. (51)
c13cc0
Moist
CI3CCOCI + I A
Anhydrous Ph3CCHCHOH
Figure 1.3.5.1.1: Reaction of trichioroacetyichioride with benzene with both anhydrous and moist
Aid 3
1.3.5.2 Side Effects
The high catalytic activity of aluminium chloride, i.e. its high Lewis Acid
strength, 52 brings certain disadvantages. Aluminium chloride can give rise to side
Chapter One
reactions, such as intramolecular migration of alkyl groups, (53) or the removal of alkyl
groups, especially tertiary groups. (54) (Scheme 1.3.5.2.1)
CH3 CH3
COCH3 Aid 3
a-i3coa
R
C(CH3)3 CI-131, C -10
A1a3 II Qi3dOQ
C(CH3)3 C(CH3 )3
Scheme 1.3.5.2.1: Example of intramolecular migration and removal of alkyl groups
Other side effects include the replacement of halogen atoms, and the splitting
of ortho-alkoxy groups, both within the acyl halide and within the substrate.
1.3.5.3 Other Metal Halides
Other highly active metal halides recommended for use in acylation reactions
include A1Br3 , FeC13, FeBr3, SbCI 5 , SbC13, TiC14, GaC13, TeC14, TeC12, ZrC14, and
ZnC12 . Some Of these halides give yields which are comparable to those obtained with
aluminium chloride.
Aluminium bromide and iodide are both active catalysts, but aluminium
fluoride has been shown to be inactive in acy1ations. 5" An example of the use of
aluminium bromide (16) is shown in Scheme 1.3.5.3.1
10
Chapter One
CH3
CH3 OCH3
COCl CH3 CH3 +
Co
CH3 CH3
OCH3
Scheme 1.3.5.3.1: Reaction of 1-acetylmesitylene with anisole using AIBr 3 as a catalyst
In a comparison of the effectiveness of the aluminium halides, (") it was found
that their effectiveness depends upon the reaction, but that aluminium iodide is more
useful for alkylation than for acylation. The iodide also makes the products difficult to
purify because free iodine is formed in small but significant amounts.
Cod 0 II
I + a A113,j II
Scheme 1.3.5.3.2: Formation of benzophenone using A113 as a catalyst
Dermer 57 ' 58 investigated a series of halides for their effectiveness in the
acylation of toluene with acyl chloride. He found the sequence to be A1C1 3> SbCI5>
FeCI3> TeCl2> SnC14> TiC14> TeC14> BiC13> ZnC12. This sequence generally holds
true for the simpler aromatic compounds, but when the aromatic substrate becomes
more complicated different metal halides work better than others. Examples of the
reactions catalysed by some of the mentioned metal halides 593 are shown in Table
1.3.5.3.1.
11
Chapter One
CATALSYST ACYL COMP AROMATIC PRODUCT REF.
FeC13 CH3COC1 m-xylene (CH3)2C6H5 COCH3 59
GaC13 CH3COCL benzene acetophenone 60
MoC1 5 CH3COCI toluene CH3C6H5COCH3 61
SbC13 C6H5COC1 benzene benzophenone 62
SbC15 C6H5COCI benzene benzophenone 62
SnC14 CH3COCI toluene CH3C6}{5COCH3 57,58
TeC12 CH3COC1 toluene CH3C6H5 COCH3 57,58
TiC14 CH3COC1 toluene CH3C6H5COCH3 57,58
ZnC12 CH3COC1 benzene acetophenone 63
Table 1.3.5.3.1: Table of metal halides and the reactions they catalyse
1.3.5.4 Metals
Some metals in their powdered form have been used as effective acylation
catalysts in conjunction with acyl halides, usually in the absence of solvents, and at
elevated temperatures. The metals which have been used are Zn, Cu, Ce, Mo, Al, W,
and Fe. Examples of some of the reactions which involve their use are shown below in
Table 1.3.5.4.1.
CATALYST ACYL COMP AROMATIC PRODUCT REF
Zn, Ce Phthalyl Cl benzene anthraquinone 64
Cu, Mo, Fe Benzoyl Cl toluene 4-methylbenzophenone 64
Al, Mo, W Benzoyl Cl m-xylene dimethylbenzophenone 64
Table 1.3.5.4.1: Table of metals and the reactions they catalyse
12
Chapter One
Their mode of action is not understood, but in the case of the electropositive
metals Zn, Al, and Fe, it appears probable that the corresponding metal halide is first
formed.
1.3.5.5 Acids
Mineral acids have been used in special cases with significant success. Acids
such as concentrated sulfuric acid, HCI0 4, and HOS02 have been the most widely
used, and the mechanism probably involves the formation of the free acylium cation.
In the diagram shown below, an example of the use of two of these acids 65 is shown.
(RCO)20 + HC104 RCO + RCOOH + C104• (5)
RCOC1 + AgC10 4 ' RCO + AgC1 + C104 (6)
RCOC1 + H2SO4 RCO + HCl + HSO4 (7)
CH3
CH3
+ (CH3CO0 H2SO4
CH3 N
CH3 NCOCH3
OCH3 OCH3
I 1 + (CH3CO)20
COCH3
Scheme 1.3.5.5.1: General reaction scheme using mineral acids as catalysts, and examples of
specific reactions in which they are used
13
Chapter One
A series of phosphoric acids; .H3PO4 (100% and 85%), H3P03, H2PO3F, and
H4P207, have been shown to be effective in the acylations of thiophene and furan. 66
~S3 + (CH3CO)20
P acid IL,
COCH3
II II + (CH3CO)20 Pacid [111
OCOCH3
Scheme 1.3.5.3.2: Acylation of thiophene and furan using phosphorous acids as the catalyst
Weaker acids, such as alkanesulfonic acid, sulfoacetic acid, p-toluenesulfonic
acid, have been less successful in acylation reactions, and the more powerful the acid
is, the more chance there will be a successful reaction.
1.3.5.6 Non-metallic Catalysts
Boron trifluoride, and its complexes with ether, methanol, and acetic acid are
pre-eminent among non-metallic halides capable of catalysing acylation reactions.
Li + (CH3CO)20 BF3
S COCH3
COCH3
I II + CH3COF I II
Scheme 1.3.5.6.1: Acylation of thiophene and benzene using BF3 as the catalyst
In the second example shown (67) the acyl fluoride is probably converted by the
catalyst into acylium fluoroborate, [CH3CO 4 ] [BF4 }, which then attacks the substrate.
14
Chapter One
The chloride (68) and bromide (69) of boron are both active catalysts, but they are
not as effective, or their use as widespread as the trifluoride. The chloride reacts best
with anhydrides, and the bromide with acids, in conjunction with aluminium chloride
or tin chloride.
Phosphorous pentachioride has been used in the benzoylation of naphthalene,
and phosphorous chloride on its own, 70 or in conjunction with zinc chloride, has
been used more widely, and with some success. (71)
Trace amounts of iodine have proved to be useful catalysts for the acylation of
reactive substrates, such as anisole, 72 thiophene, 73 and mesitylene. 74
1.3.6 Acyl Component
The acyl component in Friedel-Crafts acylation reactions may be any
substance capable of being converted into a potential acylium cation, or other reactive
entity, under the influence of a catalyst or heat alone.
For the introduction of an acyl group into an aromatic nucleus, RCOC1 is the
most frequently used, but other reagents which can be used are carboxylic acids,
esters, and anhydrides, as discussed.
1.3.6.1 Acyl Halides
The reactivity of the acyl halides when used in conjunction with aluminium
chloride has been shown to decrease with the increasing electronegativities of the
halogens. 55 This makes the order of reactivity RCOI> RCOBr> RCOC1> RCOF, and
this sequence generally holds for the simple reactions with benzene, anisole, and
15
Chapter One
mesitylene. As the aromatic substrate becomes larger and more complex, the
maximum reactivity is generally found with the bromide or the chloride.
The organic R group in an acyl halide can be almost any organic fragment, for
example, unsaturated aliphatics, hetero-aliphatics, and polycyclic arenes. Generally,
the simpler the R group, the higher the yield achieved in the reaction. For example, in
the acylation of toluene using aluminium chloride 75 the order of reactivity for three
acyl chlorides was acetyl chloride> benzoyl chloride> 2-ethylbutyl chloride.
For the simplest R groups, aluminium chloride and the acyl chloride, are
generally used. Replacement by acyl bromides has resulted in improved yields in some
cases, but the chloride is generally used.
1.3.6.2 Anhydrides
The use of anhydrides is common, and two mechanisms exist in their use. In
the first only one of the acyl components is used , whilst in the second both acyl
components are used.
(RCO)20 + 2A1C13 RC00A1C12 + RCOCLAIC13
(RCO)20 + 3A1C13 2RCOCLA1Cb + AIOC1
Scheme 1.3.6.2.1: General reaction scheme using anhydrides and A1C1 3
There are two factors which govern which mechanism operates; first the
amount of catalyst used, and second the reactivity of the acyl group. The more
reactive the acyl group, the more likely both components will be used, providing there
are three or more moles of catalyst used.
16
Chapter One
When a mixed anhydride is used the situation becomes more complex,
especially if a deficiency of catalyst is used. This means that only one of the acyl
residues will become activated.
RCOOCOR' + 2A1Cb 10 RCOCLAlCl + R'COOA1Cl2
Scheme 1.3.6.2.2: General reaction scheme using a mixed anhydride
If sufficient catalyst is used, then both acyl residues will be activated, and two
products will be formed, reactivity permitting. For example when benzoic acetic
anhydride was reacted with benzene in the presence of aluminium chloride,
benzophenone and acetophenone were obtained. 76
COC 6H5 COCH3
r') (C6H5CO)O(CH3CO) + L) + 16
7% 12%
Scheme 1.3.6.2.3: Reaction of benzene with benzoic acetic anhydride in the presence of A1C1 3
1.3.6.3 Acids
Acylation using carboxylic acids and aluminium chloride has occasionally
proved attractive, providing the substrate is inert to the catalyst, and when the acid
chloride or anhydride is obtained only with difficulty. (77)
The acylation of phenols using carboxylic acids and anhydrous zinc chloride is
known as the Nencki Reaction, 78 ' 79 but this reaction often gives low yields and
undesirable by-products. (80)
17
Chapter One
OH a + CHCOOH zna2
OH OH
+ rCOCH3
C OCR3 2-10%
2-10%
Scheme 1.3.6.3.1: Nencki Reaction, acylation of phenol using acetic acid and A1C1 3
This reaction has been largely superceded by three newer acylation
procedures. The first uses boron trifiuoride, 81 ' 82 the second uses polyphosphoric acid
(PPA), 83 ' 84 and the third is known as the Fries Rearrangement (see later), which does
not use an acid as the acyl component.
OH OH
II + RCOOH PPA
L1jJ >70%
COR
OH OH
+ RCOOH BF, I
I >70%
COR
Scheme 1.3.6.3.2: Two newer methods for the acylation of phenol using PPA and BF 3
BF3 tends to work better for polycyclic phenols than the PPA. The yields
achieved are excellent, there is little decomposition, and the work up and purification
of the products is easily achieved.
1.3.6.4 Esters and Ketenes
The use of an ester as an acyl component results in both alkylation and
acylation of the aromatic substrate, as in the case of ethyl acetate reacting with
18
Chapter One
benzene in the presence of aluminium chloride. Two products are obtained,
ethylbenzene and acetophenone.
Ketene has been used as the acyl component with some success, usually using
aluminium chloride as the catalyst, as in the reaction of ketene with benzene, anisole,
or naphthalene (85,86)
COCH3 C2H5
+ CH3COC2H5 + Ala3
IN
acylation alkylation
COCH3
+ CH2=C=O A103
I 1 ketene
Scheme 1.3.6.4.1: Acylation of benzene using an methyl ethylester and ketene
1.3.7 Houben-Hoesch Reaction
In synthesising hydroxyaryl ketones from phenols and nitriles, Hoesch noted
the difficulties encountered in preparing this class of compound, either by the normal
Friedel-Crafts method using polyhydric phenols and acyl chlorides, or by the Nencki
method using phenols and carboxylic acids. These routes often led to compounds
which had more than one acyl group.
In a series of publications, Gattermann 8793 showed that aromatic aldehydes
are readily prepared by reaction of aromatic compounds with HCN, in the presence of
HC1 and aluminium chloride. This reaction is now known as the Gattermann Reaction.
19
Chapter One
OH OH OH
HCN &CH=NRHCI
IN
HO
LCH=o I II
(H A103)
HO HO >
Scheme 1.3.7.1: Gattermann Reaction, preparation of aromatic aldehydes
Hoesch 9497 modified the reaction using nitriles instead of HCN, and replaced
aluminium chloride with zinc chloride. Houben (9"101 then made a thorough
investigation into the scope and limitations of the reaction between aromatics and
nitriles. From then it has been used principally with polyhydric phenols and their
ethers.
OH OH NH.HC1
RCN L{cR
HO Ha. za2
HO
OH NH OH 0
C' R
'& R HO> HO
Scheme 1.3.7.2: Acylation of polyhydric phenols using RCN and ZnC1 2
The reaction is known as the Houben-Hoesch Reaction, and the mechanism is
thought to occur via electrophilic attack of a carbonium ion in a normal aromatic
substitution process.
20
Chapter One
e R—C=N + IN R—C=NH
OH OH H
NH if R II ____________________
HO +
HO H
I II C'
/ OH NH
HO"& 11
Scheme 1.3.7.3: Mechanism of the attack of RCN on polyhydric phenols
1.3.8 Fries Rearrangement
Fries attempted to find a method which was more suitable than the Friedel-
Crafts method for the preparation of oriho-chloroacetyl phenols. He achieved good
results with the phenolic esters of chioroacetic acid and aluminium chloride, (111,112)
and in this way he prepared ortho- and para-chioroacetyl phenols. Fries also observed
a similar rearrangement in the case of the phenolic esters of acetic acid." 2
21
Chapter One
OH OCOCH2C1 OH
COCH2C1 Ala3
COCH2C1
OH OCOCH3 OH
Ala3 COCH3
AKi3
COCH3
Scheme 1.3.8.1: Fries Rearrangement of the phenolic esters of, chioroacetic acid and acetic acid
The Fries Rearrangement can be expressed in general terms by the reaction
below.
ArOCOR HOArCOR
where R = acid, Ar = phenolic
Scheme 1.3.8.2: General equation of the Fries Rearrangement
Although phenols may be acylated directly using aluminium chloride and acyl
halides, these ortho- and para-hydroxyketones are more frequently synthesised using
the Fries Rearrangement. ' 13 This is a reaction whereby an ester of a phenol is
transformed into an ortho- or para-hydroxyketone, in the presence of aluminium
chloride.
OCOR OH OH a J _COR +
COR
Scheme 1.3.8.3: Synthesis of ortho- and para-hydroxyketones using the Fries Rearrangement
22
Chapter One
The overall preparation requires two steps from the phenol, i.e. preparation of
the ester and the rearrangement. However the yields are usually better than those
obtained by direct Friedel-Crafts acylation of the phenol. The normal procedure is the
action of aluminium chloride on the ester in nitrobenzene for several hours and then
rearrangement. Aluminium chloride is the normal catalyst used, although SnC4,TiC1 4 ,
FeCl3, and ZnC12, have been shown to be active. (114)
Although the reaction produces a mixture of two products, they can
frequently be separated by distillation. The composition of the ratio of isomers can
depend on the reaction conditions employed, as in the case of the rearrangement of
meta-cresyl acetate, 115 in which the ratio depends upon the temperature employed.
Other experimental variables, such as solvent and proportion of catalyst can also
influence the product ratio.
1.4 Conclusion
Friedel-Crafts and related reactions are widely used as synthetic tools in
organic chemistry. The essential reaction discovered by Friedel and Crafts has opened
up a large area of related reactions and syntheses, all of which have had large areas in
the scientific literature devoted to them.
The Fnedel-Crafts Aromatic Ketone Synthesis has been shown to vary widely,
with large numbers of species able to take part in the reaction. The variety of
catalysts, aromatics, and acyl components is vast, and the number of reactions they
can take part in is huge.
23
Chapter One
2 CLUSTER CHEMISTRY
2.1 Introduction
The term cluster is commonly defined as a metal complex with two or more
metal atoms mutually bonded to each other. As such, the first clusters to be identified
were metal chioro-salts of the type W 2C193 and Re3 C1 123 which led to the realisation
of the existence of metal-metal bonds within complexes. A second class of clusters
the metal carbonyls, were later discovered with the emergence of the X-ray structural
characterisation of Fe 2(CO)9 in 1939,(' 16,117) and later the characterisation of
Mn2(C0) 10 in 1963.(h18) This represented the first example of an unsupported metal-
metal bond in this area of chemistry. Interest in the subject grew with the possibility of
producing new structural types, and this area developed further with effort being
focused on the reactivity of these species with small organic molecules e.g. alkynes,
alkenes, and arenes, to form a large number of compounds, the nature of whose ligand
co-ordinations were precisely defined by solid state X-ray molecular structures.
Muetterties 119 postulated that these bonding modes may not be too dissimilar to
those observed on metal surfaces as found in catalysts, and hence this led to their
proposition as possible models for heterogeneous catalysis and chemisorption, and
this postulation became known as the Surface Cluster Analogy.
2.2 The Surface Cluster Analogy
Although metal carbonyl clusters have been found to act as catalysts, ' 20 for
example [Fe(p.3-00)( 5-05H5)]4 in the hydrogenation of alkynes to alkenes, and
Ru3(CO) 1 2 in the water gas shift reaction, they have not to date found major industrial
application. The analogy of clusters as models for catalysis is now no longer regarded
as totally plausible, although as a model of chemisorption it has been widely applied.
Indeed, a few years after his original proposal, Muetterties 21 published a detailed
24
Chapter One
and critical review of the analogy with respect to chemisorption. This work is now
considered below.
The geometry of a cluster and a surface are usually not comparable, although
notable exceptions to this are the metal frameworks observed for some of the higher
nuclearity clusters: [Rh 13(CO)H3] 2 , [0s ioC(C0)24]2 , and [Rh14(C0)25]4
(124) which represent fragments of hexagonal close packed, cubic close packed, and
body centred cubic lattices respectively (Figure 2.2.1). However, a flat metal surface
cannot be adequately modelled by the square and triangular faces which are exhibited
by these and other polyhedral clusters. It has been suggested that they could act
instead as models for films or small particles on solid supports rather than as single
metal crystals. However, when using spectroscopic methods to study the products
resulting from chemisorption processes on poorly defined surfaces such as these, in
which the geometry of the surface is random and not ordered as in crystalline samples,
problems arise in the interpretation of the vibrational data. Because a range of
possible sites are present on which adsorption could occur, assignments of vibrational
modes can be ambiguous. Hence such systems tend not to be studied.
(a) fRhl3(CO)24H3)2 ' (b) (OsiC(CO)24) 2 (c) (Rh14(CO)25]
h.c.p. C.C.P. b.c.c.
Figure 2.2.1: The molecular geometries of the clusters [Rh 13(C0)24H3]2 , [Os1oC(CO)24] 2 , and
[Rh14(CO)1.
25
Chapter One
Even though comparable geometries are possible in clusters and surfaces,
further problems arise from the co-ordination number of the metal atom to its
neighbours, and from the metal-ligand connectivity. The co-ordination number is
usually much greater for an atom on a metal surface, typically six to nine, than for an
atom in a cluster which shows a metal-metal connectivity of two for triangular, three
for tetrahedral, and four for an octahedral geometry. The co-ordination number only
approaches that for the surface in some of the larger polyhedra such as
[Rh13(CO)24-13 ] 2 with a co-ordination of five, and a maximum of seven in the cluster
[Rh 14(CO)25 ]4 . This difference results from the close packing of metal atoms in the
bulk and their co-ordination to atoms in the sub-layer. The metal-ligand connectivity
is comparatively larger for the cluster, in the region three to five, than for the surface
which is typically one or less, and again highlights some incompatibilities between the
two regimes. Of particular importance is that the local atomic and electronic structure
of a surface is influenced by other atoms in the layer and sub-layers, for which there is
no possible cluster analogue.
Theoretical calculations have shown that a cluster of metal atoms becomes
metal-like only with nuclearities in the range 13-19 for Ni and Pd and 30-5 1 for
Ag. 112 However, these large metal-like structures show properties which are
dissimilar to the bulk metal, and only approach a truly bulk metallic state with higher
nuclearities.
A consideration of these factors clearly shows that a cluster and a metal
surface are quite distinct in nature. Hence, it is not possible to consider a cluster to
closely model a metal surface. However, the Muetterties analogy was not based on
this, although it is often misconstrued, but rather considered the "comparison between
a discrete or molecular metal cluster which has a polyhedral metal core and a
periphery of ligands, and a metal surface with a similar set of ligands chemisorbed at
the surface". Thus, it is suggested that there is no real difference in the metal-ligand
bond formed in these two extremes. Indeed, calculations have shown that it is
26
Chapter One
reasonable to approximate the adsorption of a group of atoms or a single molecule as
involving the interaction with only a small group of metal atoms, although longer
range interactions are important. For example, experiments have shown that, the
binding energy of CO on an array of Ni atoms is not greatly affected by the size of the
array. (126) The co-ordination of the ligand to a cluster is thus representative of similar
plausible co-ordination types on metal surfaces, and indeed appropriately substituted
clusters have been prepared which show many of the known adsorbate geometries. (127)
Clusters can therefore be regarded as reasonable models of chemisorbed
species on metal surfaces.
The techniques of surface analysis have in the past been considered to be
somewhat imprecise. However, as technological advances have been made, and new
techniques introduced, problems such as spectral resolution have been overcome, so
that for example using the vibrational techniques (1211 RAIRS (Reflection Absorption
Infra Red Spectroscopy) or DRIFTS (Diffuse Reflectance Infra Red Spectroscopy),
JR spectra can typically be recorded to 4 cm' resolution, although EELS (Electron
Energy Loss Spectroscopy) can only give a Ca. 10 cm-1 resolution. However the
interpretation of such data is not always straightforward, and hence a number of
techniques are usually combined to give complementary information. The comparison
of a proposed adsorbate type and co-ordination geometry with that observed in a
cluster has often proved a valuable technique in such analyses.
Chemisorption processes at metal surfaces fall into two main classes:
associative, in which there is no fragmentation, and dissociative, which results in
bond cleavage of the chemisorbed fragment e.g. dissociation of H2 gives M-H, and
examples of these processes have been reported for clusters. Likewise, mobility can
be considered as dissociative or non-dissociative. The mobility of ligands has been
established by NMR for clusters, for example the interconversion of Ru6C(C0)i1(11 6-
C6H5Me)(93 - n2 :ii 2 : i2-C6H5Me) and Ru6C(CO) i i(i6-C6HsMe)2129 and carbonyl
27
Chapter One
scrambling in M3(CO) 1 2 (M= Fe, Ru, Os). (130) The techniques of field ion microscopy
and more recently the pioneering work of Bradshaw "31 on PLEEM (Photoemission
Low Energy Electron Microscopy) have shown the mobility of ligands on metal
surfaces. PLEEM is one of the most fascinating, innovative and important techniques
to have been conceived in surface science, and has allowed the migration of molecules
on metal surfaces to be observed and recorded in real time on video tape.
Only two general examples of the analogy are cited below to typify its
application, although many others have been reported, 132 and its applicability to
surface science has proved to be helpful in interpreting a range of vibrational data.
The view of Ertl ("' ) is that the analogy although imperfect, ' 34 works for structure
and bonding but does not extend to reactivity and catalysis.
2.2.1 Chemisorption of Ethylene on a Pt(111) Surface
EEL spectra were recorded by Ibach et a! (135) for the adsorption of ethylene
on a Pt(1 11) surface at low temperature and at room temperature. Two quite distinct
spectra were observed at these temperatures, and were postulated to result from a di-
c; adsorbed species (a) and an ethylidene species (b) respectively (Figure 2.2.1.1)
H3 H3C H
H2C—CH2
Pt Pt Pt7Pt
Pt a b
C
Figure 2.2.1.1: Proposed bonding modes of ethylene on Pt (I 11)
28
Chapter One
Subsequent LEED (Low Energy Electron Diffraction) studies 11161 led to the
room temperature species being reassigned as the ethylidyne species (c). These
species were further justified by a detailed analysis of the vibrational spectra (IR and
Raman) of the cluster models C O3(CO)9( .t3 CCH3)u 37) and Os2(CO) 8(t2-CH2CH2)'38
which show analogous bonding modes (Figure 2.2.1.2).
H3
/\ (CO)3Co - 7CO(CO)3
(CO)3
H2C—CH2
/ \
(CO)40s Os(CO)4
Figure 2.2.1.2: The model clusters CO3(CO)9(.t3-CCH3) and 0s2(CO)8(j.t-C2144).
2.2.2 Co-adsorption of Benzene and CO on Rh(111)
An interesting example of the surface cluster analogy arises from the LEED
pattern observed for the co-adsorption of benzene and carbon monoxide on a Rh( 111)
surface (139) (Figure 1.2.4), and the comparable bonding mode observed for the cluster
species M3(CO)9(.t3 -C6H6) (M=Ru,Os) ( 140,141) and Ru6C(CO) i j(ii6-C6H6)(t3 -
C6H6)(l 4 la 42) (Figure 2.2.5). The benzene ligand shows co-ordination to a three-fold
site and a rehybridisation of the it orbitals so as to maximise their interaction with the
metal orbitals. This results in the shorter double bonds of the Kekulé benzene lying
directly above the metal centres and the bending of the C-H bonds away from the
metal centres. However, conflicting results have been reported which suggest that the
benzene molecule is adsorbed at a single rather than three-fold metal site and shows
no Kekulé distortion. (143)
29
Chapter One
Rh(lI 1)-(3 x 3)-C6H0 +2C0 II
Rh( 11 I)-02(3) 112 X4}re0.C6H6 + CO
Figure 2.2.2.1: The LEED pattern observed for the co-adsorption of benzene and CO on a)
Rh(1 11)- (30) C6116 + 2 CO surface, and b) Rh(1 1 1)-c(2(3) x4)rect - C 6!!6 + 2 CO surface.
Ru
Ru7tu
Ru Ru 7M M-
Figure 2.2.2.2: The structures of M3(C0)9(.L3-C6H6) (M=Ru,Os), and Ru6C(CO) 31 (p.3-C611)( 6-
C6H6).
Although the JR spectra of the benzene ligand bound to the aforementioned
clusters has been briefly reported, ( '44) a detailed comparison with the vibrational data
for the surface species has apparently not been examined.
Chapter One
2.3 Trinuclear Cluster Arene Chemistry
2.3.1 Introduction
Recently arene cluster chemistry has begun to emerge as an important entity
within the field of organometallic cluster chemistry, although the roots of this subject
date back as far as the 1960's. There is a rich chemistry associated with the arene
ligand in mono- and dimetallic compounds, and complexes of virtually every transition
metal have been prepared. Several review articles concerned with the synthesis and
structure of these compounds have been published.' 45 ' 50
Until recently relatively little effort has been directed towards the arene ligand
and its interactions with cluster complexes. The interest has been focused on arene
clusters of cobalt, ruthenium, and osmium.
Early approaches to arene cluster synthesis involved the direct reaction of the
metal carbonyl with the appropriate arene under refiux. Recently other synthetic
routes have been devised and will be discussed later.
The reactivity of arene clusters has centred on both nucleophilic substitution
reactions on the metal core, and on the aromatic ring.
The clusters produced are diverse, and many different bonding modes of the
arene ligands have been observed. The bonding modes 71 2, 116 and I.L312:12:fl2 have
been observed directly°45148 and others have been postulated. The 93-fl2:12:12 type
has been studied extensively, both on its own and its interconversion to the i6 mode.
31
Chapter One
2.3.2 Structures and Bonding Modes
2.3.2.1 Facial
The facial bonding mode of the benzene ring in the complexes 0s 3(CO)9(p.3 -
71 2:i2 :
112-C6H) and Ru3(CO)9(3-if:112:i2-C6116) are shown in Figure 2.3.2.1.1.
/
Figure 2.3.2.1.1: Facial bonding mode in 0s 3(CO)9(i.L3-11 2 :71 2 :71 2-C6H6) and Ru3(C0)9( 3-7f:1 2 :12-
C)
The bond lengths in these complexes in the benzene ring resemble that of the
hypothetical 1,3,5-cyclohexatriene molecule. The bonds are alternatively long and
short, with the short bonds being those in which the two carbon atoms concerned
interact with the one metal atom.' ° The bond lengths are 1.41A and i.siA in the
Os complex, and 1.41A and 1.45A in the Ru complex. The H molecules were located
directly in the Ru complex, and the C-H bonds were observed to bend out of the C 6
plane away from the Ru triangle by between 21.10 and 21.50 respectively. The
benzene ring and the metal triangle are almost parallel to one another.
The electronic structure of 0s3(C0)9(.t3-112:i2:i2-C6H6) has been subjected to
an ab initio calculation and an MO analysis. ( ... ) The interaction of the benzene with
the Os triangle can be rationalised in terms of donation and back donation, which is
32
Chapter One
favoured by C-H bending. The distortion of the benzene has been attributed to
enhanced back donation, and a decrease in exchange repulsion due to the it-electrons
of the benzene.
2.3.2.2 Apical
The apical bonding mode is shown below in the cluster Os 3(CO)7(93 -
C2Me2)(i6-C61-16).
Figure 2.3.2.2.1: Apical bonding mode in Os3(CO) 7( 3-C2Me2)(16-C6H).
The benzene ligand is now in a terminal position and is bound in the 116
bonding mode. The alkyne bridge is bound to the cluster by two cr interactions and
one it interaction. The average bond length in the benzene is 1.39A, which is shorter
than that in the facially bound ligand.° 52
2.3.3 Synthesis
A large number of arene clusters contain a trinuclear metal framework, and
they have recently been reviewed by Johnson et
The triosmium cluster Os3(CO)9(93-i 2:i2:ii2-C6H6) was the first example of a
cluster found to contain a facially bound arene ring. It was reported along with the
related hexaruthenium cluster Ru6C(CO)u(i 6-C6H)(.t3-i 2 :i 2:i2-C6H4."41 The
33
Chapter One
related hexaruthenium cluster Ru 6C(CO) 11 (16-C6H6)(t3-rl2 :r 2 :r 2-C6H). 141 The
synthetic route to the Os cluster begins with the complex H0s3(C0)9(t3-7i 2 :i 1 :ii 2-
C6H7) which was synthesised from H 20s3(C0) io and 1 , 3 cyclohexadiene. ( 1 S4)
sz:j octane octane Os
0s3(CO) 12 go H20s(CO)10 + 1,3-C6H8 H2, heat heat
OHOs
H0s3(CO)9(C6H7)
Scheme 2.3.3.1: Formation of HOs3(CO)9(3-i 2 :11' :1 2-C6H7)
The complex can also be synthesised from the reaction of 0s 3(CO) io(MeCN)2
with 1,3-cyclohexadiene, and the reaction proceeds via the intermediate cluster
Os3 (CO) io(r14-C6H8). (154b,1 55)
2 eqs Me3NO 0s3(CO)12
MeCN go
Os
MeCN MeCN
0s3(C0) 1 0(MeCN)2
Os 1,3-C6H8
o( Os
Q~, 0s3(CO)10(C51-18 )
S=1 IS
octane
OHOs heat
H0s3(C0)9(C6H7)
Scheme 2.3.3.2: Formation of H0s3(CO)9(,.t3-i 2 :i' :11 2-C6H7) via the intermediate cluster
0s3(C0) 10(14-C6H8)
34
Chapter One
The resultant complex HOs3(CO)9(43-1 2 :1':rl 2-C6H7) can then be converted in
two steps to the desired product Os3(CO)9(.t3-ri 2 :rl 2 :Tl 2-C6H6).
cl [ri3cI[BF4j 1 +
DBU Os Os Os
H L OHOs] o( >Os
[HOs3(CO)9(C6H6)] 0s3(CO)9(C61-16)
Scheme 2.3.3.3: Formation of 0s3(CO)9(43-i 2 :r, 2 :11 2-C6H6)
A hydride is firstly extracted from the facially bound cyclohexadienyl .ring
using the trityl cation [Ph 3C], which yields the cationic benzene cluster
[H0s3(CO)9Q.13-11 2 :i2 :i2-C6H6)1. This cluster is then deprotonated with the non-co-
ordinating base DBU to give the desired product 0s3(CO)9(.t3 -i2 :11 2 :if-C6H6).
The analogus Ru cluster R11 3(CO)9(13 -11 2 :11 2 :ri2-C6H6) was prepared five years
later, (140b) and the reaction scheme was based upon the activated Ru 3(CO) io(MeCN)2
cluster as the hydrido analogue H2Ru3(CO) io of H20s3(CO) io is not available. The
route is shown on the next page.
35
Ru 2 eqs MC3NO
Ru3(CO)12 MeCN Ru Ru
{eCN MCCN
Chapter One
heat
Ru3(CO) 10(MeCN)2
1,3H8 2 eqs Me3NO
1,3C6H
Ru H _Ru
HRu3(CO(C6H7)
[ph3q[BF4 ]
Ru
Ru H _Ru
[HRu3(CO)9(C6H6)J
DBU
Ru Ru
Ru3(CO)9(C6H6)
Scheme 2.3.3.4: Reaction sequence to form Ru 3(CO)9(43-12 :1 2 :ri2-C6H)
36
Chapter One
The route parallels that of the Os analogue, but several more convenient steps
have been incorporated and used. Firstly, I ,3-cyclohexadiene reacts directly with the
Ru3(CO) 1 2 in the presence of two equivalents of amine oxide to yield the clusters
Ru3(CO)9(93-1 2 :11 1 :11 2-C6H7) and Ru3(CO)9Q.3-71 2 :11 2 :11 2-C6116) in one step. The dienyl
cluster can then be converted into the benzene cluster by thermolysis in hexane, giving
a much simpler overall synthetic route. The Os cluster will not react in the same way,
and it has to follow the route in Figures 2.3.3.1, 2.3.3.2, and 2.3.3.3.
2.3.4 Reactions
In the scheme below, there are shown a number of reactions that have been
carried out on the Os3(CO)9(.t3-ri 2 :ri 2 :ii 2-C6H6) cluster.
o,osr
[0s3(C0)9(C6H6R1
os Os-Os
11 JABHEI3)or
4J H4] [Os I
[0s3(C0)9C6H7
[ri 3g[BF4 )
0s3(CO)(C6H5R)
0s3(CO)9(CA)
D4Et20
HBF4.EtO
~=l Os
H0s3(CO)9(C6H7)
4]
Os
O H OS
[1i0s3(C0)9(C6H6)1+
Scheme 2.3.4.1: Reactions on the arene ring of Os3(CO)9(3-i 2 :ii2 :i 2-C6H.6)
37
Chapter One
A detailed study into the reactivity of the benzene ring on the cluster
Os3(CO)9(p3-T1 2 : 2 :i12-C6H6) has recently been carried out. (156)
The increased electrophilic nature of the coordinated benzene ring favours
reactions with nucleophiles in nucleophilic substitution reactions. Good hydride
donors such as Li[BHEt 3] and [NEt4}[BH4] react easily in TI-IF to form the dienyl
cluster [Os 3(CO)9(t3-i2 :i' :i 2-C6H7)f. Exo attack of the hydride has been established
by deuterium labelling experiments.
The benzene cluster can be regenerated by abstraction of hydride from the
anionic cluster [Os3(CO)9(t3-i1 2 :1:i2-C6H7)1 - on treatment with [Ph3C][BF4]. The
anionic cluster can also be protonated with HBF 4 .Et20 to yield the neutral cluster
HOs3(CO)9(p3-TI 2 m':rl2-C6H7), which upon treatment with [Ph 3C][BF4] undergoes
hydride extraction to form the cationic cluster [HOs3(CO)9(L3-1 2 :112 :112-C6H)]. This
cluster can also be generated by treatment of the parent cluster Os 3(CO)9(p 3-i 2 :i 2 :i 2-
C6H6) with HBF4.Et20, which is reversible with DBU.
The cluster Os3(CO)9(3-71 2 :1 2 :12-C6H6) undergoes reaction with the
nucleophilic reagents MeLi and PhLi in THE This results in the substituted
cyclohexadienyl clusters [Os3(CO)9(,.13-11 2 :i1 :112-C6H6R)f, which are a result of exo
addition. Further treatment with [Ph 3C][BF4] results in the neutral clusters
Os3 (CO)9(93-71 2 : : 12-C6H5R).
These reactions display a marked similarity to those for ri6-arenes bonded to a
single metal complex.
Reactions can also be carried out on the metal framework of the parent
Os3(CO)9(43-71 2 :112 :ri2-C6H6) cluster, and they usually involve the replacement of a
carbonyl ligand by acetonitrile.
38
Chapter One
Os Me3NO Os C2H4 Os
O( Os_ O Os MeCN Os
Os3(CO)9(C6H6)
R R
/ Os
Os Os0
Os3(CO)8(C6H6)(MeCN) 0s3(CO)8(C6H6XC2H4)
Me37/"
C2R2 Os
MeCN—O( Os-
0S3(CO)7(C6H6XC2H4)(MeCN)
0s3(CO)7(C6H6XC2R2)
Scheme 2.3.4.2: Reactions on the metal triangle of Os3(CO)9(3- 2 :i2 :11 2-C6H6)
Treatment of the benzene cluster with trimethylamine N-oxide in the presence
of acetonitrile yields the cluster Os3(CO)8(43-71 2 :112 :r1 2-C6146)(MeCN). Treatment of
this cluster with a two electron donor ligand, such as tertiary phosphines and alkenes,
result in the displacement of the acetonitrile and formation of derivatives with
equatorial substitution. The co-ordination mode of the benzene ring is retained. In a
typical reaction, ethylene will react with Os3(CO)8(t3-71 2 :ri2 :n2-C6H6)(MeCN) to
produce the cluster 0s 3(CO)8(.t3 -r1 2:i2 :i2-C6H6)(i1 2-C2H4), in which the ethylene
group occupies an equatorial position on the cluster framework. 1157
The substituted cluster Os 3(CO)8(93 - 2 :1 2 :1 2-C6H6)(T 2-C2H4) will undergo
further carbonyl substitution if reacted with amine oxide and acetonitrile to produce
the cluster 0s3(CO)7(j.i3-i 2 : r12:i 2-C6H6)(ii 2-C21-L)(MeCN). This cluster reacts readily
with alkynes [RCCR'] to form the clusters 0s3(CO)7(p.3-i 2-C2RR')(q 6-C6H6). In this
cluster the benzene has now migrated to a terminal position, and the Os triangle is
face capped by the alkyne." 58
39
Chapter One
Although the Ru3(CO) 12 cluster does not undergo substitution reactions,
treatment with . alkynes in refluxing dichioromethane results in the cluster
Ru3(CO)7(i3-1 2-C2RR')(T1 6-C6H6), which is analogus to the above Os cluster. (14)
2.3.5 Conclusion
The Surface Cluster Analogy, although flawed, does show that clusters can be
regarded as reasonable models for chemisorbed species on metal surfaces. New
surface techniques, when used in conjunction with clusters, can give, a useful insight
into what happens at a metal surface.
With the combined effort of synthesis and spectroscopic methods the field of
arene cluster chemistry has expanded greatly in recent years. Newer techniques in
their synthesis are now much more selective than before. Indirect methods in which
molecules are bonded and then chemically modified are providing useful routes into
previously unobtainable arene clusters. Nucleophilic addition reactions dominate in
the reactions of arene clusters, just as they do in the chemistry of mononuclear arene
complexes.
40
Chapter One: Introduction
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Chapter One: Introduction
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44
Chapter One: Introduction
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45
Chapter One: Introduction
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Chapter One: Introduction
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Chapter One: Introduction
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48
Chapter Two
Chapter Two
2.1 Introduction
2.1.1 Palladium Complexes And Their Use In Synthesising CO/alkene Co-
polymers
The discovery in the late 1940's by Reppe and Magin" of a nickel catalysed
co-polymerisation of CO with ethylene to yield a CO-ethylene co-polymer generated
considerable interest. Significant attention was focused on these polyketones because
of the low cost of the CO feedstock. The CO accounts for half the weight of the co-
polymer, thus there are significant savings in the cost of the polymer in comparison
with poly alkenes.
Until recently, reactions to create 1:1 co-polymers gave random co-polymers,
and very few of these contained 50% weight of CO. Developments in transition metal
chemistry has regenerated the interest in these systems, and has led to the discovery of
new catalytic systems capable of producing high molecular weight, strictly alternating
polyketones.
In 1982 Sen and Lai (2) discovered that the palladium complex,
[Pd(CH3CN)4]BF4 .nPPh3 (n = 1-3), catalysed the co-polymerisation reaction of
ethylene or norbornadiene with CO.
[Pd(CH3CN)4] BF4 . n PPh3
ICH2CH2J CH2=CH2 + CO
1000psi, 250C, CHC13 n
Scheme 2.1.1.1: The copolymerisation of CO with ethylene at 1000psi
The synthesis was the first to yield a polymer with a CO:ethylene ratio of 1:1,
with the CO accounting for 50% of the weight of the polymer.
Chapter Two
In a later paper (' ) they were able to use the same complex,
[Pd(PPh3)(CH3CN)4.] BF4 (n = 1-3), to make the same reaction proceed at a lower
pressure of 300 psi.
[Pd(PPh3)(CH3CN)n 41 BF4 11
CH 2=CH 2 + CO ICH2CH2 0; 300psi, 250C, CHC13 n
Scheme 2.1.1.2: The copolymerisation of CO with ethylene at 300psi
They found the complex where n = 2, was the most effective and they
proposed a mechanism for the formation of the co-polymer.
0 0
Pd CO
Pd C2H4
Pd
0 0
CO C2H4 PdH
0 0
Coil. Pd'
C2H.4
[ 0
Scheme 2.1.1.3: The proposed insertion mechanism in the formation of (CCOCH 2CH2CH2)
In their mechanism they propose that the polymer is formed by the alternate
addition of CO and ethylene into the growing polymer chain. They argued that the CO
inserts into the preformed Pd-alkyl bond because of the greater binding ability of the
CO compared to the ethylene, and because there is a greater local concentration of
CO. The mechanism leads. to the possibility for of stepwise build up of the co-
polymer, with control over each step.
50
Chapter Two
Understanding the mechanism of the insertion process is important with regard
to developing new catalytic systems, and improving on those already established.
Subsequent work has investigated this stepwise control over the polymer build up by
investigating different palladium catalysts, and their reactions with alkenes and CO
In 1990 Brumbaugh el al. 4 investigated the insertion of norbornene and
norbornadiene into the complex [(PPh 3 )2Pd(CH3CN)(COR)] (R = Me, Et, Ph).
L Ph3P\ Pd
,COR BF4 + ,
Ph3P CH3CN
+ r Ph3P\
Pd
L p3'
Scheme 2.1.1.4: The insertion reaction of norborene into the Pd-acyl bond
They found that when the R group was electron withdrawing group, i.e. Ph,
the complex was unstable, but when the R group was electron donating, i.e. Me or
Et, the complex was stable for several days.
The crystal structure of the complex revealed that it had a square planar
structure, with the two tnphenylphosphines occupying cis positions, and the 2-
acetylnorborn- l-yl acting as a chelating ligand by coordinating through the norbornyl
carbon and the carbonyl oxygen. Until this point these types of olefin insertion into a
metal-carbon bond had rarely been reported. There are three main factors preventing
51
Chapter Two
the formation of these complexes, although they are thermodynamically favoured.
Firstly the complexes can decompose to secondary products through fl-hydride
elimination. Secondly the products derived from multiple insertions are formed, and
thirdly, kinetic barriers prevent the reaction from taking place.
Similar types of palladium complexes but with bidentate phosphine ligands
were synthesised (6) and their reactivity with a range of alkenes was investigated. (" The
simple complexes (P-P)Pd(CpCH 3)(C1) (where P-P = 1 ,2-bis(diphenylphosphino)
ethane (dppe), 1,3-bis(diphenylphosphino)propane (dppp), and 1,4-bis(diphenyl
phosphino)butane (dppb) reacted with both norbornene and norbornadiene to yield
the inserted acyl complexes.
P\
Pd
,COCH3 norborene I
Lv" CI aD2Cl2
[[>d / cH3 J + Cl.
Scheme 2.1.1.5: The reaction of (P-P)Pd(COCH 3)(C1) with norbornene
They found the reaction rate to be dppbdppp>dppe. They also found that the
reaction proceeded better and in higher yields if the complex was made ionic by
substituting a PPh 3 ligand for the Cl, and by adding silver triflate to produce the
complexes [(P-P)Pd(COCH3)(PPh3)1 + S03CF3 . These complexes would undergo
insertion reactions with a larger range of alkenes, including styrene, 1 -pentene,
norbornene, and norbornadiene.
r COCH3 OTF I CH3
OC' 1.pcnten OTf
[) ( e \ /
L C3CN]
E
[ 112
Scheme 2.1.1.6: The reaction of (P-P)Pd(COCH 3)(CH3CN) with 1-pentene
52
Chapter Two
This enabled the reactions to proceed at ambient pressure and temperature
yielding the desired CO-inserted products. The extra stability exerted by the bidentate
phosphine ligands seems to account for the ease at which the reaction proceeds.
Around the same time de Graaf et al. 8 ' 9 synthesised the analogous Pd
complexes with bidentate nitrogen ligands, instead of bidentate phosphine ligands.
CH3\ /CH3
CH
k Pd ligand = tetramethylethylene diamine (tmeda
CH( "CH3
Figure 2.1.1.1: The complex (tmeda)Pd(COCH 3)(I)
Markies et al.'° made the bpy equivalent complex of the above, and then
reacted both complexes with norbornene and dicyclopentadiene to investigate any
differences in reactivity between the two
N COCH3 LN><I
bipyridyl COCH3
N G N
"'Pd\ I
53
Chapter Two
N COCH3 r N COCH3 1
/ A8OTf OTFPd r >d \ CH3CN /
LN L 'N CH3CN]
norbomenc \di.yclopentadienc
+
CH3
[
+ 0Tf
[
]OTU
FN1 — N
= tmeda and bpy L = bpy only N
Scheme 2.1.1.7: The reaction of [(bpy)Pd(COCH 3)(CH3CN)]OTf with norborene and
dicyclopentadiene
They discovered that the bpy complex is the more reactive of the two, reacting
with both the norborene and the dicyclopentadiene whereas the tmeda complex only
reacts with the norborene.
They found that the reactions would only proceed in the presence of silver
triflate, indicating that the reaction proceeds via ligand dissociation of the acetonitnle,
proceeded by formation of complex. The precipitate formed in the reaction was
identified as AgI, further confirming that the reaction proceeds via the mechanism
shown in scheme 2.1.1.7.
This type of system, using the complex (bpy)Pd(COCH3)(I), was developed
further to allow the controlled stepwise build up of a CO/alkene co-polymer."
0 54
Chapter Two
+ OTF
cOcH3 I COCH3 AgOTf ~-N
"Pd CH3CN
CH3CN norbomene
-1 + OTf CH3
(
O ,
f y CO, NaX
I I I 'Pd
-
/
OTf aectone
N' X UIJ 0 ' othoe
+
OTf
Scheme 2.1.1.8: The stepwise build up of a CO/norborene co-polymer using the complex
(bpy)Pd(COCH 3)(I)
The reaction is a controlled stepwise build up of the CO/alkene chain, using 1
equivalent of the complex to produce a polymer. The inserted complex with the five
membered Pd-acyl ring is synthesised as before with acetonitrile, silver triflate, and
norbornene. The resultant complex then undergoes further CO insertion in the
presence of a large excess of sodium halide, Cl or I. This complex can then undergo
further insertion of norborene, allowing the stepwise build up of the CO/norbornene
co-polymer.
55
Chapter Two
2.1.2 Industrial Background
The work specifically in this chapter was funded by Zeneca in Grangemouth,
where they have recently built a new fiuorobenzene plant. This plant currently runs at
around 50% capacity, and they were specifically interested in the reactions of
fluorobenzene to produce two target molecules. These complexes offered the
possibility of using up some of the spare capacity of the plant.
The first target molecule was the acylated derivative of fiuoroben.zene, with
the acyl group in either the ortho- or the para- positions. The reason behind the work
was to find an alternative catalyst to aluminium chloride because of environmental
considerations.
COCH3 COCH3
ortho para
Scheme 2.1.2.1: Ortho - and para- acylated fluorobenzene
The aim was to synthesise this molecule by inserting an acyl group into
fluourobenzene by the use of a bidentate N-N Pd complex. This meant progressing
the previous work from simple alkenes, and investigating its usefulness with regard to
aromatics, specifically fluorobenzene.
56
CM3 oC,
CJN/\X O
O.CH3
F
acylated fluorobenzer
COCH '-r "Pd" (NV \ MeCN
AgOTf
OTf -
+
OTf -
CO-1/ NaX
Chapter Two
1+ r CH3
I ' Pd OTf
I
, \ AgOTf,Q{, LO' F U 7 7
Scheme 2.1.2.2: Insertion of fluorobenzene into the complex (bpy)Pd(COCH 3)(I)
If this inserted acyl complex could be made, it is postulated that it may be
possible to separate the 'acylated' fluorobenzene and set up a catalytic cycle,
regenerating the Pd complex for further reaction, with the complex becoming a
catalytic reagent.
Scheme 2.1.2.3: Catalytic cycle for the production of acylated fluorobenzene
57
Chapter Two
In the first stage of the reaction the fiuorobenzene inserts into the Pd-acyl
bond forming a five membered metallocycle with the palladium. The complex would
then undergo a further CO insertion, before the acylated fiuorobenzene is separated,
and the catalyst regenerated. This proposal results in the formation of acylated
fiuorobenzene catalysed by the complex {(bpy)Pd(COCH3)(I)}.
The second of the target molecules was the 4-4 'difiuorobenzophenone shown
below in figure 2.1.2.1.
a I F"
II
Figure 2.1.2.1: 4,4'-difluorobenzophenone
This molecule is currently synthesised by Laporte using fiuorobenzene and
phosgene in the reaction shown below.
0 F F
+ cIcI F
4,4 70%
4,2 15%
4,3 10%
Scheme 2.1.2.4: Synthesis of difluorobenzophenone
Chapter Two
The main drawback with the reaction is that it is not stereospecific. The yield
of 4-4'difluorobenzophenone is 70%, and the remaining 30% of the products are of
little use to the chemical industry. Laporte currently manufacture and sell 700 tonnes
per annum of the 4-4' difluorobenzophenone to polymer manufacturers to synthesise
the polymer Victrex (PEEK).
1 II
F)C 1OF 0 n
VICTREX (PEEK)
Scheme 2.1.2.5: The reaction of 4-4' difluorobenzphenone to produce the polymer Victrex
Zeneca wanted to be able to make the starting material, 4-4'
difluorobenzophenone for £10-12 per kg, thus undercutting the Laporte price of
£20/kg. This would give them the option of making it themselves, or selling the
technology to Laporte with a tie in deal to buy the fluorobenzene exclusively from
them.
The palladium complex{(bpy)Pd(COCH3)(I)} is also postulated to be a
catalyst in the synthesis of the polymer PEK. The proposed synthetic route is shown
below in Scheme 2.1.2.6. The starting material for the synthesis is
(bpy)Pd(CODPE)(I), which is converted as before to the ionic complex
{(bpy)Pd(CODPE)(CH 3CN)}OTf This complex is then reacted alternately with DPE
and CO to build up the polymer PEK.
59
Chapter Two
N. CODPE
NI I + cao DPE
MCCN! AgOTf
1+ DPE
o c/
I OTC
N/
N
NaX
1+
1 0 0 OTf I ii
N ,C)LDpEl o nPd
[
N"
% X
j
PEK
Scheme 2.1.2.6: Potential use of a Palladium complex to produce the polymer PEK
2.2 Reactions of (bpy)Pd(COMe)(I) with Cyclic Alkenes and Dienes
A dichioromethane solution of (bpy)Pd(COMe)(I) was cooled to 0 °C. To the
solution was added acetonitrile, silver triflate, and cyclic alkene or diene, and a yellow
solid of silver iodide immediately precipitated out of solution. The solution was stirred
for three hours before being filtered, and the solvent removed under vacuum. The
product was identified on the basis of mass spectrum and IR.
Me
Chapter Two
Results and Discussion
In Table 2.2.1 the relevant spectroscopic data is shown.
Cyclic Diene or Alkene Product MS/amu ER (CO)/ cm'
Cyclohexene { (bpy)Pd(C6H1 000Me) }(OTf), 1 M = 387 1690
1,3-cyclóhexadiene {(bpy)Pd(C6H8COMe))(OTf), 2 M = 385 1682
1,4-cyclohexadiene {(bpy)Pd(C6H8COMe)}(OTf), 3 M 385 1656
1,5-cyclooctadiene {(bpy)Pd(C6H12COMe)}(OTf), 4 M = 389 1654
Table 2.2.1: Spectroscopic data for acyl inserted Pd complexes
All of the products were identified on the basis of their mass spectra, which all
showed the parent ion peak at the expected value. The resultant complexes are shown
below in figure 2.2.1
/ CH3
IN\ Pd
oC
{(bpy)Pd(C 6H8COMe)) 0T1 3
+ _+ CR3
OTF OTf
flPd
{(bpy)Pd(C 6H8COMe)}OTf 2
CH3 O '
N C OTF
N / [ 'Pd
'
{(bpy)Pd(C 8HCOMe)} OTf 4
IN\ Pd
o C/ CR3
{(bpy)Pd(C 6HCOMe)} OTf 1
+
OTf
Figure 2.2.1: The complexes from in the reaction with { (bpy)Pd(COCH3)(CH3 CN) }OTf
61
Chapter Two
The complexes are all unstable in the presence of an inert gas. This contrasts
with previous work with the alkenes norbornene and dicyclopentadiene, where the
complexes have been described as being stable in air for several days at room
temperature. 9 In this case all the solutions begin to turn black upon addition of the
alkene or diene. The black colour comes from elemental palladium precipitating out of
solution. The JR shows the presence of a peak for the COCH3 peak at around 1600-
1 700cm', indicating that the desired complexes have been formed.
The solutions were left to stir for several days until all the elemental palladium
precipitated out of the solution. The solution was filtered and reduced under vacuum,
leaving no evidence of any of the desired complexes being formed.
Conclusion
The complex (bpy)Pd(COCH3)(I) will react with cyclic alkenes and dienes to
form the resultant acyl inserted complexes. These complexes however, are
unexpectedly unstable, even in the presence of an inert gas. The complexes are
probably unstable due to the five membered metallocycle of the alkene or diene. This
part of the complex is physically strained making it unstable, and this instability
probably results in the whole complex falling apart.
2.3 Reactions Of (bpy)Pd(COMe)(I) with Arenes
A dichloromethane solution of (bpy)Pd(COMe)(I) was cooled to 0 °C. To the
solution was added acetonitrile, silver trifiate, and cyclic alkene or diene, and a yellow
solid of silver iodide immediately precipitated out of solution. The solution was stirred
62
Chapter Two
for three hours before being filtered, and the solvent removed under vacuum. The
products were analysed for their Mass Spectra and 1W.
Results and Discussion
Below in figure 2.3.1 are shown the complexes that were hoped to be
synthesised by this route.
CH3 oc,
IN le ~~b
+ I CH3 OTf Oc/
Pd I rN I I
LN
+
OTf -
{(bpyPd(C 6H6COMe)}OTf 5
Oc/ CH3 oTF
IN ,Pd B
{(bpy)Pd(C 6H3rCOMe)) 0T1 7
r CH3 OTf I o"
I N / IN\ Pd
H3j
{(bpy)Pd(C 6H5MCCOMe)} 0T1 9
((bpy)Pd(C 6H5FCOMe)} OTf 6
{(bpy)Pd(C 8H8COMe)} OTf 8
CH3 i r N
O' OTf / 0H
IN.' \ I HO
{(bpyC6H4(OH)2COMC)} OTt 10
+
OTF
Figure 2.3.1: The expected complexes from the reaction with {(bpy)Pd(COCH3)(CH3CN)}OTf
63
Chapter Two
In the case of the above complexes there is no evidence of their formation in
either the IR spectrum or in terms of mass spectroscopy. There are no peaks at the
expected range of 1600-1700cm' for the IR, and their is no evidence of any parent
ion peak in the mass spectrum.
In each of the reactions there is a large degree of decomposition with
elemental palladium precipitating out of solution. The decomposition in these
reactions also happens more quickly than in the reactions with the alkenes and the
cyclic dienes, making analysis difficult. These complexes are expected to be much
harder to form than the alkene type complexes because of the strength of the aromatic
C-C bond..
Conclusion
There is no evidence for the formation of the desired palladium complexes
with arene rings. The strength of the aromatic C-C bond appears to be prevent the
acyl insertion. This part of the work was the least likely to be successful as this type of
insertion into an arene ring is not a known reaction. However, after finding evidence
for the formation of the alkene and diene complexes it was attempted with the
industrial aim of the thesis in mind.
2.4 Reaction of (tmeda)PdCl 2 with Phenyl Lithium
A solution of (tmeda)PdC1 2 suspended in diethyl ether was cooled to -30T
using an acetone/CO 2 bath. The stirred solution was treated with PhLi and was
allowed to warm slowly to 0°C. The resultant solution was stirred for 1 hour, before
ice cold water (lOml) was added. The organic layer was separated and dried over
MgSO4, and the solvent was removed under vacuum. The product was identified as
the starting material (tmeda)PdC1 2 on the basis of 'H nmr and mass spectra.
64
Chapter Two
Results And Discussion
H 5/ppm
2x -N(CH3)2 2.54 (s, 6)
2x -CH2- 2.26 (s, 4)
Table 2.4.1: The NMR results of the reaction
In the 'H NMR the appearance of only two peaks indicates that the starting
material, (tmeda)Pd(Cl)2, has been formed. This is confirmed by the mass spectra
which has a parent ion peak at 291amu.
The aim of the reaction was to synthesise the complex (tmeda)PdPh 2, 11,
which could then be reacted with CO to produce benzophenone as shown below in
scheme 2.4.1
N Ph %% / Co Pd
'Ph Ph-Ph
Scheme 2.4.1: The reaction of (tmeda)Pd(Ph)2 to produce benzophenone, palladium, and tmeda
Previous work by De Graaf et. al. 8 has shown that the similar complex
(tmeda)PdMe2 would undergo a reaction with CO. yielding acetone, tmeda, and
palladium.
65
Chapter Two
1—N /CH3 d6-benzene I /Pd\
l LN CH3
eqCO
0 II + Pd + tmeda
CH3CH3
tmeda
Scheme 2.4.2: Reaction of (tmeda)Pd(CH 3)2 to produce acetone, palladium, and tmeda
The reaction was undertaken in d 6-benzene, and the aim was to attempt to
repeat the reaction with two phenyl groups instead of the two methyl groups. If the
reaction was possible, it may then have been possible to attempt the reaction with a
stereospecific lithium para-fluorobenzene, making the reaction generate the desired
target complex 4-4' difluorobenzophenone.
rN Cl
I Pd + LN Cl
Li
F
F
10 [Pd
N / \
0 F
11
[Pd Co
IN
FF + Pd + tmeda
Scheme 2.4.3: Possible synthetic route for the synthesis of 4-4'diflnorobenzophenone
Chapter Two
The data form the 1H nmr and the mass spectra indicate that attempts to form
the complex (bpy)Pd(Ph)2 have failed, with only the starting material evident in the
analysis. This failure is most likely explained by the large size and steric bulk of the
two phenyl ligands making it impossible for both to occupy cis positions around the
palladium metal.
Conclusion
It is not possible to form the complex (bpy)Pd(Ph)2 as a possible reactant to
produce benzophenone. The steric bulk of the arene ring prevents its formation.
2.5 Conclusion
The complex (bpy)Pd(COCH3)(I) has been shown to react with simple cyclic
alkenes extending previous work with simple alkenes. The work however was not
able to be further extended into allowing the complexes to react with benzene and
substituted benzenes. This meant that the industrial aim of the project of setting up a
catalytic cycle producing an acylated fluorobenzene, and regenerating the palladium
complex (bpy)Pd(COCH 3)(X), were not able to be achieved
Attempts to synthesise the second industrial target molecule 4,4'-
difluorobenzophenone also failed. The proposed synthetic route via the complex
(bpy)Pd(C6H4F)2 was not possible as the steric bulk of a phenyl ring is too large to
occupy the cis positions on the Pd metal centre.
67
Chapter Two
2.6 References
W. Reppe, A. Magin, US Patent 2,577,208 (1951)
A. Sen, T.-W. Lai, J. Am. Chem. Soc., 1982, 104, 3520
A. Sen, T.-W. Lai, Organometallics, 1984, 3, 866
J.S. Brumbaugh, R.R. Whittle, M. Parvez, A. Sen, Organomelallics, 1990, 9, 1735
J.P. Coilman, L.S. Hegedus, J.R. Norton, R.G. Finke, Principles andApplications of Organotransition Metal Chemistry, University Science Books, Mill Valley, CA, 1987
G.P.C.M. Dekker, C.J. Elsevier, K. Vrieze, P.W.N.H. van Leeuewen, Organometallics, 1992, 11, 1598
G.P.C.M. Dekker, C.J. Elsevier, K. Vrieze, P.W.N.H. van Leeuewen, CT Roobeek, .J. Organomet. Chem., 1992, 430, 357
W. de Graaf, J. Boersma, W.J.J. Smeets, A.L. Spek, G. van Koten, Organomelallics, 1989, 8, 2907
W. de Graaf, J. Boersma, G. van Koten, Organometallics, 1990, 9, 1479
B.A. Markies, M.H.P. Rietveld, J. Boersma, A.L. Spek, G. van Koten, J. Organomet. Chem., 1992, 424, C12
B.A. Markies, M.H.P. Rietveld, J. Boersma, A.L. Spek, G. van Koten, K.A.N Verkerk, H. Kooij man, .1. Chem. Soc., Chem. Comm., 1993, 1317
Chapter Three
Chapter Three
3.1 Introduction
In chapter one the bonding of a benzene ring to an Os or Ru three atom
cluster in the face capping and apical modes was discussed. A benzene, or more
generally an arene, can also bond to a cluster in the benzyne bonding mode.
C(114) C(115)
Q116)
C(111) 0003)
Ci
0(23) __-- C(33,1 CL 0(21)
C(23) -
=IO(C3(
) 0(13)
C(
Figure 3.1.1: Crystal structure of 0s 3(CO)9(H)2(C6H4)
In the above structure the benzene is bonded to the cluster through two of the
ring carbons. The benzene is bound through two a bonds and one it bond, over the
face of the cluster. The ring is at an angle of between 63.9° from the plane of the
cluster. The ligand is a four electron donor, donating one electron each to Os(1) and
Os(2) via the two a bonds, and two electrons to Os(3) via the it bond.
This type of cluster was first synthesised by Deeming and Underhill (2) directly
from the reaction of 0s3(CO)12 with benzene at 200 °C. More recently clusters of the
type Os3(CO)(L)(,.13:i1 2 :i12 :112-C6H) have been shown to undergo conversion to the
benzyne complexes of the type
We
Chapter Three
The Os(1)-Os(2) distance is long, 3.026(2)A, considering that a metal-metal
bond is present, and it is very similar to the Os-Os bond in the complex
0s3(C0) 10(0Me)2 This cluster has two -OMe bridges and the Os-Os distance of
3.078(2)A is for a formal bond order of zero. 4
The fragment 0s(1)(.t-H)C(1 1 1)C(1 12)0s(2) is best considered as a
delocalised bonding unit.
C C
/ \ Oszr------Os
Figure 3.1.2: The delocalised bonding unit OsQ.-H)CCOs
Bridging metal hydrides, in the absence of other bridging groups, usually result
in the M-M bond being lengthened." When a second bridging group, with a single
bridgehead atom is added, the M-M bond is usually found to be shortened. (' ) If the
second bridging group has two bridgehead atoms the shortening effect is less
pronounced, as in the case of the cluster Os 3(t-H)(CO) io(C3H3N2). 7
(CO),
(CO)3 OS OS (CO)3
f c N H
Figure 3.1.3: The bonding mode of Os3(1.-H)(CO) 1 o(C3H3N2)
In the benzyne cluster there is no shortening effect, and instead a lengthening of
0.05A is observed, when compared to the hydride bridged Os-Os bond of 2.989(1)A
in the cluster 0s3(9-H)2(C0)10. 8
70
Chapter Three
The benzyne ligand is able to adapt to span various metal-metal edges in
cluster species. The Os-Os bond length of 3.791(1)A in the cluster H0s3(C0)9Q.t-
H)-SMe)(C614) 9 represents the Os-Os bond which is bridged by the benzyne and
the -SMe group. The thiol group is a three electron donor, and this causes the Os-Os
bond to lengthen.
0 Os— -H
/7 \I
Me
Figure 3.1.4: The bonding mode of 0s 3(C0)9(4-H)(j.t-SMe)(C 6H4)
The Os-Os bond length of 2.866(2)A in the benzyne cluster
0s3(C0)9(H)2(C61Q is bridged by a hydride, but is slightly shorter than the Os-Os
distance .of 2.877(3)A in the parent cluster, 0s 3(C0) 12 .' 8 This suggests that the it
interaction of the benzyne ligand on Os(3) has a shortening effect on the Os-Os
distance. A similar influence appears on the unbridged Os(2)-Os(3) bond which, is
shortened by around 0.03A compared to the parent cluster 0s 3(CO) 12 .
In their paper Johnson et al also reported the synthesis of aryne clusters in
which the ligands used were substituted benzenes such as toluene. ( ' ) The substituted
aryne clusters are thought to exist in four different isomeric forms.
71
Chapter Three
R
r\R
Os-- H
__ / \ i Os-Os
a
R
R R//\\ f
1' 8
Figure 3.1.5: Four isomeric forms of 0s 3(CO)9(H)2(C6H3R)
The first proposals were that the isomers resulted from a ring flipping
mechanism which is occurring rapidly on the NMR timescale at room temperature.
The mechanism was also postulated as possible exchange between two different
forms, i.e. a exchanging with y, and 0 exchanging with 6. This means that the ring is
in a fixed position, and that it is the hydrides that are exchanging, resulting in only two
isomeric forms."
'H NMR studies carried out by Shapely and Kneuper' ° using spin saturation
techniques have led to the postulation that the hydrides on the cluster are fluxional,
and also exchange with those on the benzene ring.
72
Chapter Three
Figure 3.1.6: Exchange mechanism of hydride and arene proton
In the proposed exchange mechanism the bridging hydride moves from a site
bridging a pair of Os atoms to a site associated with a pair of electrons between a C
and an Os atom. This creates an agostic three centre two electron bond of C-H-Os.
The arene ligand then rolls so that a new C-H-Os bridge is created while the other is
broken. Exchange is completed by proton migration back to the Os-Os site creating a
new Os-H-Os bridge. Some it bonding or interaction between the aryl and the Os
framework is maintained throughout the reaction.
73
Chapter Three
3.2 Reactions of 0s3(C0), 0(MeCN)2 with Substituted Arenes
Following on from the work of Johnson et al,' a series of substituted benzene
aryne complexes were synthesised and their crystal structures investigated.
3.2.1 Reaction of 0s 3(C0),0(MeCN)2 with Arenes of the Type C 6115R (where R =
F, Cl, Br, and CR3)
An arene solution of 0s3(CO),o(MeCN)2 (13) was heated under reflux for 1
hour before being left to cool to room temperature. The solution changed from yellow
to dark brown after reflux. The arene was removed under vacuum and three main
products were separated chromatographically using hexane as eluant. In order of
elution these products were identified as unreacted cluster 0s 3(CO),o(MeCN)2 (13),
0s3 (CO) 12 (12), and 0s3(C0)9(t-H)2(C6H3R) (14, 15, and 17) and 0s3(C0), o(p.-Br) 2
(16), on the basis of IR, mass spectrometry, and in addition for 14, 15, and 17 by 'H
NMIR. All four products were confirmed by X-ray crystallography.
Results and Discussion
JR and Mass Spectroscopy
In each case the unreacted cluster 13 and the parent cluster 12 were identified
on the basis of their IR spectra in the carbonyl stretching region, and their mass
spectra. The unreacted cluster 13 was present in 10-15% yield. Clusters 14, 15, 16,
and 17 were characterised on the basis of their mass spectra which showed the parent
ion peaks at the expected positions, followed by the subsequent loss of carbonyl
ligands. The IR spectra showed peaks in the region 2100-1970 cm' indicating that
only terminal carbonyls are present. The data are shown over the page in table
3.2.1.1.
74
Chapter Three
0s3(C0) 9(p-ll)2(C6H3F), 14
IR (vCO)I cm"
2114, 2083, 2056, 2035, 2021, 2007, 2000
MS/amu
M' = 920 (caic. 918)
0s3(C0)9(p.-H)2 (C6H3CI) 1 15
IR (vCO)I cm'
2110, 2083, 2058, 2037, 2025, 2025, 2011, 2003
MS/amu
M' = 936 (caic. 934)
0s3(C0) 10(J.L-Br)2, 16
ER (vCO)/ cm'
2113, 2082, 2053, 2014, 2007
MS/amu
M+ = 1012 (calc. 1008)
0s3(CO)9(p.-R)2(C6113C113), 17
JR (vCO)I cm 1
2109, 2079, 2052, 2033, 2022, 2002
MS/amu
M' = 918 (caic. 914)
Table 3.2.1.1: Spectroscopic data for the aryl cluster species
Cluster 16 was an attempted synthesis of the cluster Os 3(CO)9(.t-H) 2(C6H3Br),
but the IR spectrum showed no expected peak at 2035 cm 1 , as in the case of the
fluoro- and chlorobenzene derivatives. There was also an additional peak at 2053
cm'. In the mass spectrum the parent peak was thought to be M= 984 (caic. 984)
amu which indicated the desired product. However a smaller peak at M= 1012 (caic
1010) amu can be attributed to the parent peak of cluster 16, making the peak at 984
amu the peak for 16 with the loss of one carbonyl. The 'H NMR was recorded in
CD2C12 but gave only the signal for free bromobenzene. This evidence along with
crystallographic information proved that the cluster was in fact 0s 3(C0), o(.t-Br)2."
Os—Br OS•__Br___OS
Figure 3.2.1.1: The bonding mode of 0s3(CO) 1o(-Br) 2
75
Chapter Three
'H NMR
The 'H NUR of the remaining three clusters were measured in CDCI 3, and the
results are shown below.
Hb Mc Hb Mc
sHd Hd
Hd Hd
Ic
flu
14 15 15
0s3(CO) 9(1i-R)2 (C6H3F), 14 Os3(CO)9(i-H)2(C6H3CI), 15
H 6/ppm 11 8/PPM
Ha 7.63 (d) Ha 7.83 (d), 7.89 (d)
Hb 6.58 (t) Rb 6.82 (t)
Hc 6.94 (m) Hc 7.30 (d)
Hd -18.3 (s) Hd -18.7(s)
Figure 3.2.1.2: The clusters Os 3(CO) 9(pt-H)2(C6H3F) and Os 3(CO)9(-H)2(C6H3Cl) and a table of
their 'H NMR data
For cluster 14, four resonances were observed at ö values of 7.63 (1H), 6.94
(1H), 6.58 (1H), and -18.3 (2H) ppm. These resonances can be readily assigned to the
hydrogens on the fluorobenzene as shown in the diagram, and the data suggests that
the cluster exists in one isomeric form, with the F-atom occupying the site nearest to
the cluster.
The 'H NMR of cluster 15 indicates the presence of two isomers with the
observation of five resonances at 5 values 7.89 (1H), 7.83(1H), 7.30 (IH), 6.82(1H),
76
Chapter Three
The 'H NM1R of cluster 15 indicates the presence of two isomers with the
observation of five resonances at ö values 7.89 (1H), 7.83(1H), 7.30 (1H), 6.82(1H),
and -18.7 (211) ppm. The signals are assigned to the hydrogens as shown in the
diagram with the predominate isomer being the one where the -Cl atom occupies the
site nearest to the cluster, as in the case with 14.
In figure 3.2.1.3 below is the 'H NUR data for the for cluster 17.
Ha Ha
H s/ppm
Ha 7.74 (d) 7.84 (d)
Hb 6.73 (m) 6.73 (dd)
Hc 7.08 (d) 7.71 (s)
Hd 2.45 (s) 2.31 (s)
He -18.5(s) -18.9(s)
Figure 3.2.1.3: The two isomeric forms of the cluster 0s 3 (CO)9(4-H)2(C6H3CH3) and its 'H NMR
data
The 'H NMIR data for 17 indicates the presence of two isomers with the
observation of eight resonances at ö values 7.84 (111), 7.74 (1H), 7.71 (111), 7.08
(111), 6.73 (1H), 2.45 (3H), 2.31 (3H), -18.5 (2H), and -18.9 (2H) ppm. The signals
have been assigned above, and the ratio of isomers is approximately 1:4.
The observation of a single hydride resonance in each of the three spectra
implies that the hydrides are fluxional in all the complexes.
77
Chapter Three
X-ray Structure Determination
Single crystals of 0s 3(C0)9(.t-H)2(C6H3F) 14, 0s3(C0)9(t-H)2(C6H3C1) 15,
and 0s3(C0)9(t-H) 2(C6H3CH3) 17, suitable for X-ray analysis were grown from a
solution of pentane at 5 °C. The solid state molecular structures are presented in the
following pages together with some relevant bond lengths for each structure. In each
case the structure confirms that the Os trinuclear cluster framework remains intact,
and that the arene ligand is aryne bonded to the cluster framework. The carbonyls are
all terminally bound, as indicated by the IR spectrum, with three attached to each Os
atom.
A single crystal of 0s3(C0) io(t-Br)2 was also grown from a solution of
pentane at 5 T. The structure was not solved as it has been reported previously."
78
0(23) 0(31)
0(33)
0(22]
L.flupwr inre
Figure 3.2.1.4: The molecular structure for Os 3(CO) 9(-H)2(C6H3F)
Os(1)-Os(2) 2.7554(8)
Os(1)-Os(3) 2.8615(7)
Os(2)-Os(3) 3.0417(8)
Os(3)-C(2) 2.14(2)
Os(2)-C(1) 2.11(2)
Os(1)-C(1) 2.400(13)
Os(1)-C(2) 2.358(13)
C(1)-C(6) 1.42(2)
C(1)-C(2) 1.48(2)
C(2)-C(3) 1.41(2)
C(3)-C(4) 1.36(3)
C(4)-C(5) 1.41(3)
C(5)-C(6) 1.37(3)
C(1)-F(1) 1.36(2)
mean C-0 1.14
Table 3.2.1.2: Selected bond lengths for Os 3(CO)9(-H)2(C6H3F)
79
031
Chapter Three
013
Figure 3.2.1.5: Molecular structure of Os 3(CO)9(-H)2(C6H3Cl)
Os(1)-Os(2) 2.7502(13)
Os(1)-Os(3) 3.010(2)
Os(2)-Os(3) 2.852(2)
Os(1)-C(6) 2.102(11)
Os(3)-C(5) 2.152(11)
Os(2)-C(6) 2.439(11)
Os(2)-C(5) 2.298(11)
C(5)-C(6) 1.42(2)
C(1)-C(2) 1.32(2)
C(2)-C(3) 1.41(2)
C(3)-C(4) 1.37(2)
C(4)-C(5) 1.42(2)
C(1)-C(6) 1.43(2)
C(1)-Cl(1) 1.780(12)
mean C-0 1.14
Table 3.2.1.3: Selected bond lengths (A) for 0s3(CO)g(i.t-H)2(C6H30)
80
(13)
Chapter Three
Figure 3.2.1.6: Molecular structure of 0s3(CO)9()i-H)2{ C6H 3(CH3)}
Os(1)-Os(2) 2.8470(10)
Os(1)-Os(3) 3.0147(9)
Os(2)-Os(3) 2.7627(9)
Os(1)-C(76) 2.11(2)
Os(3)-C(71) 2.13(2)
Os(2)-C(71) 2.432(14)
Os(2)-C(76) 2.27(2)
C(71)-C(76) 1.36(2)
C(71)-C(72) 1.46(2)
C(72)-C(73) 1.35(2)
C(73)-C(74) 1.45(2)
C(74)-C(75) 1.36(2)
C(75)-C(76) 1.47(2)
C(73)-C(77) 1.50(2)
mean C-0 1.14
Table 3.2.1.4: Selected bond lengths (A) for Os3(CO)9(p.-H)2C6H3(CH3))
81
Chapter Three
3.2.2 Reaction of 0s 3(CO),o(MeCN)2 with C6114(CH3)2 (ortho-, meta-, and para-)
The reaction conditions utilised were as described previously, using an ortho-,
meta-, or para-xylene solution of 0s 3(CO), o(MeCN)2. For ortho- and meta-xylene,
three products were separated by TLC using hexane as eluant, and these were
identified as the unreacted cluster 13, cluster 12, and Os 3(CO)9(t-H)2 {C6H2(CH3)2}
18 and 19, on the basis of IR, mass spectrometry, 'H NMR, and X-ray
crystallography. For the para-xylene reaction two major products were separated by
TLC using hexane as eluent, and these were identified as unreacted cluster 13, and
cluster 12.
Results and Discussion
The unreacted cluster 13 and the parent cluster 12 were identified on the basis
of their IR carbonyl spectra, and their mass spectrometry. Clusters 18 and 19 were
characterised on the basis of their mass spectra which showed the parent ion peaks at
the expected values, followed by subsequent loss of carbonyl ligands. The IR
spectrum shows peaks in the region of 2100-1970 cm' indicating that only terminal
carbonyls are present. The 'H NMIR spectra were recorded in CDC1 3, and all the
spectroscopic data is shown below in figure 3.2.2.1.
U
Os3(CO),(H)2 {orth0CH2(CH3)2} 0s3(C0)9(1)2 {metaC 6H2(CH3)2 )
Figure 3.2.2.1: The bonding modes of the clusters Os 3(CO)9(-H)2 {ortho-C6H2(CH3)2} and
0s3(C0)9(-H)2{meta-C6H2(CH3)2}
82
Chapter Three
Os3(CO)9(-H)2 {ortho-C6II2(CH3)2}, 18
ER (vCO)Icm'
2107, 2079, 2053, 2033, 2022, 2006, 1997
MS/amu
M+ 930 (ca1c. 928)
1H NMR 6/ppm
Ha: 7.60 (s), Hb: 2.19 (s), Hc: -18.1 (s)
Os3(CO)9(-H)2 meta-C61I2(CH3)2), 19
IR (vCO)/cm'
2105, 2076, 2052, 2032, 2021, 2005, 1997
MS/amu
M = 932 (ca1c. 928)
'H NMR 6/ppm
Ha: 7.43 (s), Hb: 6.80 (s), Hc: 2.17 (s), Hd: 2.19 (s), He: -18.5 (s)
Table 3.2.2.1: The spectroscopic data for Os3 (CO)9(-H)2 {ortho-C6H2(CH3)2} and Os 3(CO)9(.t-
H)2{meta-C6H2(CH3)2}, and their spectroscopic data
The 'H NIvIR of 18 indicates the presence of a single isomer with the observation of
four resonances at ö values 7.60 (2H), 2.19 (6H), and -18.5 (2H).
The 'H NMR of 19 indicates the presence of one isomer with the observation
of five resonances at 6 values 7.43 (1H), 6.80 (1H), 2.19 (3H), 2.17 (3H), and -18.5
(2H) ppm.
The unreacted cluster 13 and the parent cluster 12 were identified on the basis
of their IR carbonyl spectra, and their mass spectrometry. There is no evidence for the
desired product Os 3(CO)9(.t-H)2{C6H2(CH3)2}, as shown in figure 31.2.2.
83
Chapter Three
Figure 3.2.2.2: The structure of 0s 3(C0) 9(-H)2(C6H2(CH3)2 ).
It appears that the product cannot be formed because of the steric interaction
of the two -CH3 groups with the Os cluster. Previously it has been shown, in the case
of meta-xylene, that one -CH 3 group can occupy the site closest to the cluster.
However in this case in which two -CH 3 groups would need to occupy these
positions, and the steric interaction appears to be too great.
X-ray Structure Determination
Single crystals of ortho- and meta- Os3(CO)9(..t-H)2 {C6H3(CH3)2) 18 and 19,
suitable for X-ray analysis were grown solutions of pentane at 5 °C. The solid state
molecular structure is presented together with some relevant bond lengths for each
structure. The structure confirms that the Os trinuclear cluster framework remains
intact, and that both the xylenes are aryne bonded to the cluster framework. The
carbonyls are all terminally bound, as indicated by the IR spectrum, with three
attached to each Os atom.
84
Chapter Three
031
021
Figure 3.2.2.3: Molecular structure of 0s3(CO)9(9-H)2{C6H2(CH3)2 }
Os(1)-Os(2) 2.766(3) I Os(1)-C(6) 2.38(2)
Os(1)-Os(3) 2.881(4)
Os(2)-Os(3) 3.056(3)
Os(2)-C(1) 2.10(2)
Os(3)-C(6) 2.12(2)
Os(1)-C(1) 2.30(2)
C(1)-C(6) 1.43(3)
C(1)-C(2) 1.44(3)
C(2)-C(3) 1.37(3)
C(3)-C(4) 1.40(3)
I C(4)-C(5) 1.37(3)
C(5)-c(6) 1.47(3)
C(3)-C(30) 1.55(3)
C(4)-C(40) 1.53(3)
mean CO 1.13
Table 3.2.2.2: Selected bond lengths (A) for Os3(CO)9(t-H)2[C6H2(CH3)2]
85
033
Chapter Three
021
Figure 3.2.2.4: Molecular structure of 0s3(CO)9(9-H)2 [C6H2(CH3)2]
Os(1)-Os(2) 2.7425(12)
Os(1)-Os(3) 2.8666(13)
Os(2)-Os(3) 3.0379(15)
Os(3)-C(1) 2.108(10)
Os(2)-C(2) 2.123(10)
Os(1)-C(1) 2.306(10)
Os(1)-C(2) 2.408(9)
C(1)-C(2) 1.441(14)
C(2)-C(3) 1.445(13)
C(3)-C(4) 1.39(2)
C(4)-C(5) 1.39(2)
C(5)-C(6) 1.368(15)
C(6)-C(1) 1.451(15)
C(3)-C(3M) 1.51(2)
C(5)-C(5M) 1.504(14)
mean C-O 1.13
Table 3.2.2.3: Selected bond lengths (A) for 0s3(CO)9(i.t-H)2[C6H2(CH3)2]
86
Chapter Three
3.2.3 Conclusion
From the spectroscopic and crystallographic data it can be observed that
different substituted benzenes yield different predominant isomers. The fluoro- and
chlorobenzenes yield species where the halogen occupies the site closest to the Os
cluster, i.e. the most steric hindered site. Previous studies by Deeming and Arce (12) on
the cluster { Os 3H(CO)9(AsMe2)(C6H3OMe) } have indicated that the the orientation
of the benzyne ligand is dependent on electronic effects. As the halogens are electron
donating they favour adopting the position nearest to the cluster because of the
conjugative effect on the benzyne ring. If the halogen occupies the site furthest away
there is unfavourable competition between the halogen and the metal for the benzyne
LUMO that is involved in it-bonding between the Os atom and the benzyne ligand.
When the substituted benzenes contain -CH 3 groups, the preferred site is the least
sterically hindered site, which is that furthest away from the Os cluster. A single -CH 3
group will, however, occupy the site closest to the cluster as in the reaction with
meta-xylene, but two -CH 3 groups will not occupy these sites simultaneously, as
shown in the unsuccessful reaction with para-xylene. This position of a -CH 3 group is
probably a combination of both electronic and steric effects.
A summary of the relevant bond lengths in the five structures are shown below
in table 3.2.3.1.
Chapter Three
Cluster Number -
Bond Description 14 15 17 18 19
AvOs-Os 2.87 2.87 2.87 2.90 2.88
Max Os-Os 3.042 3.010 3.014 3.056 3.038
Mm Os-Os 2.756 2.750 2.763 2.766 2.743
Av ring C-C 1.39 1.39 1.41 1.41 1.41
Max ring C-C 1.49 1.43 1.47 1.47 1.45
Nfin ring c-c 1.34 1.32 1.35 1.37 1.37
C-R 1.396 1.78 1.36 1.55, 1.53 1.50, 1.51
a-Os-C 2.11, 2.14 2.10, 2.15 2.11, 2.13 2.10, 2.12 2.11, 2.12
t-Os-C 2.36, 2.41 2.30, 2.44 2.27, 2.43 2.30, 2.38 2.31, 2.41
Ày c-o 1.14 1.14 1.14 1.13 1.13
Table 3.2.3.1: Summary of bond distances of the five crystal structures
In the crystal structures there is no great variation in the bond lengths between
the different structures. The average Os-Os distances are all in the range 2.87-2.90 A.
Each structure has one long and one short Os-Os bond, with the short bond being the
one which is bridged by the aryne ligand in the a-bonded manner. This bond is also
bridged by a hydride, and as demonstrated in the introduction, this exerts a shortening
effect on the Os-Os bond. The longest bond in each case is the one which has a
bridging hydride only, causing the bond to lengthen to 3.01-3.06 A. In each case this
means that the cluster is slightly distorted, and this is reflected in the ic-Os-C bonds. In
each structure one is longer than the other by 8-16 A. From structure to structure
there is a slight variation in the average length of the ic-bonds, which are slightly
longer at an average of 2.38 A for the halobenzenes than the average of 2.35 A for the
methylbenzenes. The a-Os-C bonds are more equal in value, with only a slight
differences in each structure.
The arene rings all have an average C-C bond length of 1.39 to 1.41 A. This
compares almost exactly to the bond length in free benzene of 1.396 A. The average
Chapter Three
C-C distances in the arene rings are slightly shorter at 1.395 A in the halobenzenes
than they are in the methylbenzenes at 1.41 A. The C-C bond lengths vary in each
structure from that approaching a C-C double bond to a C-C single bond. In four of
the structures C-C bond bridging the cluster is one of the longest, except in the case
Of Os3(CO)9(4-H)2 {C6H3(CH3)} (17) where the bridging C-C bond is short at 1.36(2)
A.
In each structure the C-R bond lengths are the normal bond lengths expected
for each structure. The average carbonyl bonds are almost identical in each structure
at 1.13-1.14 A.
In all the structures the hydride ligands were not located directly. In some the
XHYDEX programme was used to place the ligands, and in the others their position
can be determined by examination of the bond lengths.
3.3 Reactions of 0s3(C0) 10(MeCN)2 with ct-methylstyrene, Styrene, and 1,3
diisopropenebenzene
An octane solution of 0s3(CO) io(MeCN)2 (13) and the arene complex was
heated under refiux for 1 hour before being left to cool to room temperature. The
solvent was removed under vacuum and the products were separated
chromatographically by TLC using hexane as eluent.
3.3.1 Results and Discussion for Reaction with a-methylstyrene
Four main products were separated in the reaction and these wee identified as
unreacted cluster 13, cluster 12, and Os3(CO)9(.t-H)2[C 6H3(C(CH3)CH2)] 21 and 22,
Chapter Three.
by their IR and mass spectra. The unreacted cluster (13) and the parent cluster (12)
were identified on the basis of their JR spectra in the carbonyl stretching region and
their mass spectroscopy.
Compounds 21 and 22 both have similar IR spectra, and both have mass
spectra with parent ion peaks M= 941 (calc. 939) amu followed by subsequent loss
of carbonyls. This indicates that the products are very similar, and may be different
isomers of the same product. Previous work reported in this chapter has shown the
evidence for different isomers being formed, but these are not usually separable by
TLC. As the bands are very close on the TLC plate, clusters 21 and 22 may be two
different isomers of the product, as shown below in figure 3.3.1.1.
H2C
H C—CH3
H—?J5—H ,,CH
a b
Figure 3.3.1.1: The possible isomers of Os3(CO) 9(-H)2 [C6H3(C(CH3)CH2)]
Isomer a would appear to be the most likely to be formed as it is the least
sterically hindered of the two. As shown previously with toluene and the xylenes, a -
CH3 group will not occupy the site closest to the Os cluster in preference to a site
further away. This would be expected to exclude isomer b, but a possibility for its
formation is with the pendant arm parallel to the Os cluster. With the reactive
substituent in such a position it may be possible to form isomer b. As the yields are so
low the 'H NMR spectrum of the two species are too weak to assign peaks:
Me
Chapter Three
3.3.2 Results And Discussion Of Reaction with Styrene
Three products were separated by TLC using hexane as eluent. In order of
elution these products were identified as the unreacted cluster 13, cluster 12, and
Os3(CO)9(t-H)2 {C6H2(C6H3(CHCH2)) 23, on the basis of IR, mass spectrometry, and
in addition for 23, by 'H NMR.
Cluster 23 was characterised on the basis of its mass spectrum which showed
the parent ion peak at M= 926 (caic. 926) amu followed by subsequent loss of
carbonyl ligands. The JR spectrum shows peaks in the region 2100-1990 cm'
indicating that only terminal carbonyls are present. The compound may exist in the
isomers shown below.
H2C
Figure 3.3.2.1: Possible isomers of 0s 3(CO)g(j.t-H) 2 { C6H2(C6H3(CHCH2) )
The 'H NN'IR, which would be able to give structural details, is to weak to
assign because of the low yield of the cluster, but it does appear that the compound
has been formed.
91
Chapter Three
3.3.3 Results And Discussion Of Reaction with 1,3 diisopropenebenzene
Three products were separated by TLC using hexane as eluent. In order of
elution these products were identified as the unreacted cluster 13 and cluster 12 on
the basis of ER, and mass spectrometry.
The desired product with the 1,3 diisopropenylbenzene aryne bonded to the
cluster is not formed in the reaction. This is probably because of the steric interaction
of the pendant arm with the cluster.
H
Figure 3.3.3.1: A possible structure of 0s 3(C0)9(4-H)2 { C6H2(C(CH3)2) }
3.3.4 Conclusion
The evidence that the ct-methylstyrene product can exist as two isomers is not
supported by the non-reaction of the 1,3 diisopropenylbenzene with the Os cluster.
This reaction, although unsuccessful, indicates that the most likely products are those
shown below (Figure 3.3.4.1) where the reactive substituent occupies the site furthest
away from the metal cluster.
92
Chapter Three
H2C H C—H
H
H,C
Figure 3.3.4.1: Bonding modes of Os3 (CO) 9(-H)2 {C6H3(CHCH2)} and Os3(CO) 9(-
H)2 ( C6H3(C(CH3)CH2) }
With extremely low yields of the products, it has not been possible to obtain
any structural information from NMR, or from crystallography, although the products
do appear to have been formed.
93
Chapter Three
3.4 References
I.- R.J. Goudsmit, B.F.G. Johnson, J. Lewis, P.R. Raithby, M.J. Rosales, J. Chem. Soc., Dalton Trans., 1983, 2257
A. J. Deeming, M. Underhill, .1. Chem. Soc., Dalton Trans., 1974, 1415
M.A. Gallup, B.F.G. Johnson, J. Lewis, A. McCamley, R.N. Perutz, J. Chem. Soc., Chem. Comm., 1988, 1071
V.F. Allen, R. Mason, P.B. Hitchcock, J. Organomet. Chem., 1977, 140, 297
M.R. Churchill, B.G. DeBoer, F.J. Rotella, Inorg. Chem., 1976, 15, 1843
P.R. Raithby, Transition Metal Clusters, ed. B.F.G. Johnson, John Wiley and Sons, Chichester, 1980
J.R. Shapley, D.E. Samkofi C. Bueno, M.R. Churchill, Inorg. Chem., 1982, 21, 634
M.R. Churchill, B.G. DeBoer, Inorg. Chem., 1977, 16, 878
R.D. Adams, D. A. Katahira, L.-W. Yang, Organometallics, 1982, 1, 235
H.-J. Kneuper, J.R. Shapley, Organometallics, 1987, 6, 2455
B.F.G. Johnson, J. Lewis, P.A. Kilty, J. Chem. Soc., 1968, 2859
A.J.Arce, A.J. Deeming, .1. Chem. Soc., Dalton Trans., 1982, 1155
94
Chapter Four
Chapter Four
4.1 Introduction
In chapter three the synthesis of triosmium arene clusters with the arene
bonded in the benzyne mode were discussed. The benzyne cluster Os 3(CO)9(j-
H)2(C6H4), where the arene ring is bound to the metal cluster through two aromatic
carbons, is known to undergo subsequent reactions on both the arene ring, and on the
metal centre. Both types of reaction on the cluster Os 3(CO)9(j.t-H)2(C17l4) will be
discussed in this chapter. This type of work will then be extended later in the chapter
to deal with both types of reaction on the functionalised clusters 0s 3(CO)9(p.-
H)2(C6H2 R'R2) (where R' = H, R2 = F, Cl, CR3 ; R1 = CH3,R2 = CH3 ).
4.1.1 Attack on Metal Framework
The benzyne cluster, Os 3(CO)9(t-H)2(C6H4), is readily activated using
trimethyl N-amine oxide and acetonitrile to yield both the mono- and bis-substituted
acetonitrile derivatives."
I eq. Me 3NO 0s3(CO)8(MeCN)(H)2(C 6H4)
MeCN
Os3(CO)i)2(C6H4)
MeCN '
2 eq. Me3NO 0s3(CO)7(MeCN)2(H)2(C6H4)
Scheme 4.1.1.1: Reaction of 0s3(CO)9(H)2(C6H4) with 1 and 2 eqs. of amine oxide
Chapter Four
These clusters are both highly reactive and air sensitive, and they both react
readily with PPh 3 and P(OMe) 3 to yield the clusters 0s 3(p.-H) 2(CO)8(PR3)(C6H4) and
Os3(.t-H)2(CO)7(PR3)2(C6H4).
Both these clusters can also be synthesised by the photolysis of the face
capped benzene clusters Os3(CO)9(PR3)(t3-ri 2 :ii2 :ii 2 -C6116), where n = 1,2, and R
Ph, OMe.
hv/toluene Os3(CO)9..(PR3)(C6H6) 5°C ' Os3(CO)9..(PR3)(C61-I4)
Scheme 4.1.1.2: Reaction of face capping cluster Os3(CO)9(PR3)(j43-7, 2 :1 2 :11 2 -C6116) to yield the
benzyne cluster Os 3(4-H 2(CO) 9.(PR3)(C6H4)
In the mono-substituted product two possible isomers can occur, and they are
shown below in Figure 4.1.1.1.
Figure 4.1.1.1: Two possible isomers of 0s3(4-H)2(CO)8(PR3)(C6H4)
The isomers are either axial or equatorially substituted. In the case of PPh 3 ,
the major isomer is the axial substituted cluster, while for the P(OMe) 3 , the major
isomer is the equatorial substituted cluster. This is mainly due to the steric
requirements of the two types of phosphine ligand. The steric repulsion between the
Chapter Four
bulky PPh3 ligand and the C 6H.4 moiety is minimised by the PPh3 occupying the axial
position.
The bis-substituted cluster 0s 3 (j.i-H)2(CO)7(PPh3)2(C6H4) appears as only one
isomer, while the cluster Os 3(.t-H)2(CO)7 {P(OMe) 3 } 2(C6H4) appears as two isomers.
The 31P NM1R shows one signal for one of the hydrides coupling to both phosphines,
and one signal for the other hydride coupling to only one of the phosphines, indicating
the structure below for the Os 3 (t-H)2(CO)7(PPh3)2(C6H4) cluster.
Figure 4.1.1.2: Isomer for the cluster Os 3(4-H)2(CO)7 (PPh3)2(C6F4)
The cluster Os3(t-H)2(CO)7 {P(OMe)3 } 2(C6H4) exists as two isomers, and the
31P NMR indicates that the molecule is asymmetric. ( ' ) The NMR indicates that one of
the hydrides is trans to one phosphite and cis to the other, while the other hydride is
cis to only one of the phosphites.
The benzyne cluster has been shown to undergo reactions with
diphenylacetylene 2 to yield the disubstituted cluster 0s 3(CO)7(C 6H4){PhCC(H)Ph}2.
The benzyne cluster is activated by amine oxide and acetonitrile to yield the cluster
Os3(9-H)2(CO)7(C6}{4)(MeCN)2. This reactive cluster undergoes reaction at room
temperature to produce the disubstituted cluster.
97
Chapter Four
aim
fIi
040
CW Y a4 OM W
a311'lJp
cm
Figure 4.1.1.3: Molecular structure of Os 3(-H)2(CO)7 (C6H4)(PhCC(H)Ph) 2
The diphenylacetylene ligands have inserted into the two cluster hydrides, and
these are now bonded to one of the acetylene carbons. The ligands bridge an edge,
and each acts as a three electron donor, donating two electrons via a it bond, and one
electron through a a bond. Os(3) is it bound to C(29) and C(28), and Os(1) is a
bound to C(28). The cluster is a 48 electron species, with each metal atom obeying
the 18 electron rule.
The Os-Os distances are significantly shorter at 2.717(2)A for Os(2)-Os(3)
compared to 2.877(3)A in the parent cluster Os 3(CO)i2. 3 The acetylene bridge exerts
a shortening effect on the Os-Os bond distance.
4.1.2 Attack on the Arene Ring
The benzyne ligand in this cluster will undergo Friedel-Crafts acylation and
ailcylation under mild conditions, displaying the nucleophilicity of the arene ligand
despite the loss of electron density upon co-ordination to the metal cluster. (4)
98
Chapter Four
When an arene ring co-ordinates to a cluster, the electron density of the arene
will decrease and, the arene is therefore deactivated towards reaction with
electrophiles. For example, in the face capping benzene cluster Os 3(CO)9(C6H), the
co-ordinated benzene ligand easily undergoes reaction with nucleophiles, which is in
contrast to the behaviour of free benzene which favours reaction with electrophiIes."
In the benzyne cluster, although there is a loss of electron density on the arene
ligand, the cluster readily undergoes reactions under Friedel-Crafts conditions,
yielding acylated and alkylated products.
0s3(C0)9(H)2(C6H4) Rd/Aid 3
0s3(CO)9(H)2(C6H3R) 2' OoC to RI
where R= CH3 CO, or But
Figure 4.1.2.1: Acylation and alkylation of 0s 3(CO)9(H)2(C6H3R)
The products have the same JR pattern as the parent cluster, but the
absorptions shift 1-5 wavenumbers higher for acylation and 1-3 wavenumbers lower
for alkylation. This implies that electrophilic sustitution does not change the symmetry
of the molecule but does slightly change the electron density on the arene and the
cluster carbonyl ligands.
In the case of acylation, the presence of an electron withdrawing group
COCH3 decreases the electron density on the arene and the metal framework.
Therefore back donation from the metal atoms to the carbonyls is weakened, which in
turn results in stronger bonding between the C and the 0 atoms of the carbonyl. The
IR is therefore shifted to higher wavenumbers.
Chapter Four
In the case of alkylation the tertiary butyl group is weakly electron donating,
and the result is the opposite to above, weakening the bonding between the C and the
0 atoms of the carbonyl.
4.2 Reactions of Clusters Os 3(CO)9(9-H)2(C6H2R'R2) (where R' = H, R2 = F, Cl,
CH3; R' = CR3, R2 = CH3) Towards Acylation
A carbon disulphide solution of aluminium chloride and acetyl chloride was
cooled to 0 CC. A solution of 0s3(C0)9(j.i-H)2(C6H2R1 R2) in carbon disulfide was
added dropwise over 1 hour, and the resultant solution was allowed to warm to room
temperature. The solution turned pale brown upon warming to room temperature, and
the solvent was removed under vacuum. In each case one major product was
separated chromatographically using hexane/dichloromethane (1:1 v/v) as eluent. The
products were identified as 0s 3(CO)9(1.t-H) 2 {C6HR'R2(COCH3)} on the basis of IR,
and mass spectra, and in addition for 25, by 111 NMR.
Results and Discussion
In the Table 4.2.1, all the relevant spectroscopic data is shown. For the IR
spectra the peaks of the parent complexes are also shown.
100
Chapter Four
Os3(CO)94i-H)2 {C6H2F(COCH3)}, 25
IR (vCO)/ cm'
Acylated: 2116, 2085, 2058, 2038, 2024, 2010, 2002
Parent: 2114, 2083, 2056, 2035, 2021, 2007, 2000
MS/amu
M 960 (caic. 960)
Os3(CO)9(9-ll)2 C(,H2Cl(COCH3)), 26
ER (vCO)/ cm'
Acylated: 2112, 2085, 2059, 2039, 2028, 2014, 2006
Parent: 2110, 2083, 2058, 2037, 2025, 2011, 2003
MS/amu
M= 978 (caic. 976)
Os3(CO)9(-ll)2{C6H2(CB3)(COCH3)}, 27
ER (vCO)/ cm'
Acylated: 2113, 2082, 2054, 2035, 2025, 2006
Parent: 2109, 2079, 2052, 2033, 2022, 2002
'MS/amu
M+ 954 (calc. 956)
Os3(CO) 9(9-H)2 1(ortho-C6H(CH3)2(COCH3)}, 28
ER (vCO)/ cm
Acylated: 2110, 2082, 2054, 2036, 2024, 2008
Parent: 2107, 2079, 2053, 2033, 2022, 2006
MS/amu
M+ = 975 (calc. 970)
Os3(CO)9(-H)2 1(meta-C6H(CH3)2(COCH3)}, 29
JR (vCO)/ cm'
Acylated: 2108, 2078, 2054, 2033, 2023, 2008
Parent: 2105, 2076, 2052, 2032, 2021, 2005
MS/amu
M = 972 (caic. 970)
Table 4.2.1: Spectroscopic data for the acylated cluster species
101
Chapter Four
All of the products were identified on the basis of their mass specra, which
showed the parent ion peak followed by loss of carbonyls. The IR spectra in the
carbonyl stretching region are all shifted by 1-3 cm' higher energy when compared to
the parent clusters. As discussed previously this is because of the electron withrawing
nature of the -COCH 3 group, affecting the carbonyl ligands of the cluster.
IR were attempted on all of the products but there was no evidence for any
peaks in the region 1600cm' as expected for a -COCH 3 group. However the solutions
were very weak as a result of the very low yields of the reactions.
The 'H NIMIR spectrum of 25 was recorded in CD 202, and four resonances
were observed at ö values 7.84 (1H), 7.36 (1H), 2.64 (1H), and -18.3 (1H). These
resonances can readily be assigned to the protons on the fiuorobenzene ring and the
hydrides on the cluster.
Rb C—C(HC)3
Fla— ij—F
Hd
5 Hd
H 8/PPM
Ha 7.84 (d)
Hb 7.36(d)
Hc 2.64(s)
Hd -18.3
Figure 4.2.1: The 'H NMR data for 25
102
Chapter Four
The NMR data implies that the -COCH3 group occupies the position oriho to
the F atom of the ring. This is expected as -F is an ortho/para director. As the ortho
position is occupied exclusively, this indicates that the para position is sterically
hindered by the Os cluster, and the bonded carbonyl ligands.
Although no 'H NTvIR spectrum was possible for 26, the product is expected
to be the in the same configuration as 25, with the -COCH 3 group occupying the
position ortho to the -Cl on the chlorobenzene ring.
The parent toluene cluster 17 exists in a different predominant isomeric form,
with the methyl group in a position furthest away from the Os cluster. The ortho/para
directing nature of the methyl group gives two possible sites for the -COCH 3 group to
occupy, both of which are ortho to the methyl group.
,$ H3C—C CH3
OS-OS
Figure 4.2.2: The structure of 0s 3(CO)9(H)2{C6H2(CH3)(COCH3)}
As in the acylation reactions of the fluoro- and chlorobenzene clusters, one of
the two possible sites for the -COCH 3 group to occupy is hindered by the cluster. The
most likely position is that shown above with the -COCH 3 group in the ortho site
furthest away from the cluster.
To investigate further if the -COCH3 group could occupy the hindered site
nearest to the cluster, the acylation reaction was attempted on 18,
103
Chapter Four
0s3(CO)9(H)2(C6H2(CH3)2 . This complex has two vacant sites in the ortho-xylene
ring, both of which are hindered sites near to the cluster.
Figure 4.2.3: The structure of 0s 3(CO)9(H)2 {C6H(CH3)2(COCH3))
The reaction was successful, but in lower yields than the other acylated
clusters. This indicates that the site nearest to the cluster can be occupied, although
the low yield, 6%, implies that there is a steric interaction with the Os cluster.
In the acylation reaction of 19, the resultant cluster, 29, is expected to have
the -COCH3 group in a position between the two methyl groups of the meta-xylene
ring.
[-I
Figure 4.2.4: The structure of 0s 3(CO)9(H)2 {C6H(CH3)2(C0CH3)}
The reaction proceeds in yields similar to that for 25, 26, and 27, indicating
that the reaction produces the structure shown above with the -COCH 3 group in the
site furthest away from the cluster.
104
Chapter Four
Conclusion
In all the acylation reactions the IR spectra are shifted 1-3 cm' higher,
indicating the presence of a -COCH 3 group. The yields of the acylated complexes are
all very low and the 'H NMR data was only produced for one of the complexes. This
data indicated that the acyl group was occupying the position furthest away from the
cluster, indicating that the -COCH3 group is sterically hindered from occupying the
site nearest to the cluster. Although this position does not appear to be favoured, in
the acylation reaction of the ortho-xylene cluster the acylated cluster is formed. As the
methyl groups are occupying the sites furthest away from the cluster, the acyl group
must occupy a hindered site nearest to the cluster.
In general, it is assumed that the -COCH 3 group is hindered from occupying a
site nearest to the cluster, and that where possible it avoids occupying these sites.
4.3 Reaction of 0s3(CO)9(p.-H)2(C6H3F) with 2-butyne
A dichloromethane solution of 0s3(C0)9Qt-H)2(C6H3F) and excess 2-butyne
was activated by the dropwise addition of trimethylamine N-oxide and left to react
over 1 hour. The solvent was removed under vacuum and two main products were
separated chromatographically using hexane as eluant. In order of elution these
products were identified as Os3(CO)8(.t-H)(CH2CHCHCH3)(C6H3F) 30 and
0s3(CO)8(9-H)(CH3CCCH3)(C6H3F) 31, on the basis of their IR, and mass spectra,
and in addition for 31 'H NIvIR, and for 30 X-ray crystallography.
105
Chapter Four
Results and Discussion
Clusters 30 and 31 were characterised on the basis of their mass spectra which
showed the parent ion peaks at M= 945 (calc. 945), and M= 953 (calc. 945) amu
respectively, followed by the subsequent loss of carbonyls. The IR spectra of the two
species in the carbonyl region are quite similar, although cluster 31 has an extra peak
at 2057 cm". Both spectra indicate that only terminal carbonyls are present.
The 'H NMR spectra of both complexes were recorded, but in the case of 30
the sample was too weak to give a meaningful spectrum. The spectrum of 31 shows
seven resonances were observed at ö values 7.65 (1H), 6.96 (1H), 6.62 (t), 3.15 (3H),
3.00 (3H), -16.1 (1H), and -18.4(1H) ppm. Theses resonances can be readily assigned
to the hydrogens on the fiuorobenzene, and to the two -CH 3 groups of the 2-butyne.
H 8/PPM
Ha 7.65 (d)
Hb 6.96(m)
Hc 6.62 (t)
Hd 3.15 (s)
He 3.00(s)
Hf -16.1 (s)
Hg -18.4(s)
Figure 4.3.1: Cluster 31 and its 'H NMR data
106
Chapter Four
The observation of the two singlets at 3.00 and 3.15 ppm indicates that the
butyne remains intact and that the two -CH 3 groups are inequivalent. This suggests
the structure shown, with the butyne ligand replacing one of the carbonyls, and
bonding as shown. The butyne ligand acts as a two electron donor, and the cluster is
formally a 48 electron species. The signals due to the fluorobenzene ligand remains
the same as those for the parent cluster and suggests that it has not been altered. The
peaks at -16.1 and -18.4 ppm shows that there are two inequivalent hydrides in the
cluster.
This type of bonding mode with alkynes is well known in monomeric and
dimeric complexes, for example in Os(NO)(CO)(PR 3)2(PhCCPh) 6 and
Pd2C14(ButCCBut) (7)
X-ray Structure Determination Of 30
Single crystals of 0s 3(CO)g(p-H)(CH2CHCHCH3)(C6H3F) 30, suitable for X-
ray analysis were grown from a solution in pentane at 5 °C. The solid state molecular
structure is presented in Figure 4.3.2 together with some relevant bond lengths and
angles in Table 4.3.1. The structure confirms that the Os cluster framework remains
intact, and that the fluorobenzene ligand remains aryne bonded to the cluster. The 2-
butyne has undergone an H atom shift from one of the methyl groups to one of the
alkyne carbons, and has also added a further presumably cluster derived, H to the
second alkyne carbon. This generates an 3-1-methylallyl ligand which replaces one
carbonyl and one hydride ligand in the parent cluster. The remaining carbonyls are all
terminally bound, as indicated by the IR spectrum.
107
012
Os(1)-Os(2) 3.067(2) I Os(1)-C(7) 2.25(3)
Os(1)-Os(3) 2.816(2)
Os(2)-Os(3) 2.745(2)
Os(2)-C(1) 2.06(3)
Os(1)-C(6) 2.13(3)
Os(3)-C(1) 2.34(2)
Os(1)-C(8) 2.20(3)
Os(1)-C(9) 2.33(3)
C(7)-C(8)-C(9) 134(4)
C(10)-C(9)-C(8) 135(4)
C(9)-C(10) 1.34(4)
Chapter Four
032
Figure 4.3.2: Molecular structure of 0s3(CO)8(j.t-H)(CH2CHCHCH3)(C6H3F)
Os(3)-C(6) 2.23(3) I C(2)-F(2) 1.39(3)
C(1)-C(6) 1.42(3)
C(1)-C(2) 1.45(3)
C(2)-C(3) 1.32(4)
C(3)-C(4) 1.36(4)
C(4)-C(5) 1.45(4)
C(5)-C(6) 1.40(3)
mean C-0 1.167
Table 4.3.1: Selected bond lengths (A) and angles (°) for 0s3(CO)g(jt-H)(CH2CHCHCH3)(C6H3F)
108
Chapter Four
The cluster is a 48 electron species, with the butyne-derived ligand allyl
bonded to Os(1), and donating 3 electrons. A possible mechanism for the formation of
this ligand is represented in Figure 4.3.3.
Os
V \-H CH3
\ %—O
\I
s PClI
HI H H
Os V H CH3
Figure 4.3.3: Reaction of 2-butyne with the Os cluster to become an allyl group
The 1-methylallyl ligand is possibily formed in a one step process, with the
cluster hydride and the methyl proton undergoing transfer to their respective carbons,
causing the butyne to adopt an allyl bonding mode.
These 1-methyl allyl groups are generally formed using dienes or allyl halides,
not alkynes. Two well known examples are, the reaction of CoH(CO) 4 and
butadiene, (8) and the reaction of Pt(cod) 2 with an allyl halide. (9)
109
Chapter Pour
H H
CoH(C0)4 + C\ ,C, H2Cc?7CH_CI13
10
H H2 CH Co
H
Pt(cod)2 + H3C—C=C---C1 (cod)P(23
I I I Cl H H H
',
C + II/\
(cod)P\ /CH
CH
CH3
Figure 4.3.4: Formation of a 1 -methylallyl group from an alkyl halide and butadiene
In the butadiene reaction the hydride on the Co atom shifts to one of the
terminal -CH 2 groups, changing it into a -CH 3 group and causing the ligand to allyl
bond to the Co atom.
In the crystal structure of 30 the average Os-Os distance is 2.876 A, which is
almost the same as in the parent cluster 14 where the distance is 2.866 A. The butyne
Os-C bonds vary from 2.20(3) A to 2.33(3) A. The Os(1)-C(8) distance is the
shortest at 2.20(3) A, and Os(1)-C(9) is the longest at 2.33(3) A. The bond is
probably lengthened because of the close proximity of the C(1O)H 3 group to the
fluorobenzene ring. The steric interaction between the two is sufficient ot lengthen the
Os-C bond. The C(9)-C(10)H3 is very short at 1.34(4) A for a C-CH 3 bond, and is
almost approaching that of a C-C double bond.
110
Chapter Four
The bonds between the Os cluster and the fluorobenzene ring are slightly
distorted because of the butyne derived ligand. The ring has twisted slightly causing
the it-bond Os(3)-C(6) to shorten significantly to 2.23(3) A compared to 2.36(2) .A in
the parent cluster. This twisting has also shortened Os(2)-C(1) by 0.06 A to 2.06(3)
A. The other c- and it-bonds are almost the same length as in the parent cluster,
suggesting that the fiuorobenzene ring is closer, and more tightly bound than in the
parent cluster.
In the fiuorobenzene ring the C-C distances range from 1.32(4) A to 1.45(4)
A, and the C-F distance is 1.39(3) A. These compare almost exactly with those in the
parent cluster.
The carbonyls are all terminal, and have an average C-O length of 1.167 A.
This is very long compared to the parent clusters average of 1.14 A, and the longest
are those bonded to Os(1) which are 1.18(3) A and 1.20(3) A. This is due to the
presence of the butyne group, and the steric bulk of the group causes the carbonyls to
lengthen.
Conclusion
A second proposal for the mechanism for the conversion of the 2-butyne
ligand to a 1 -methylallyl ligand, which takes into account the characteristaion of both
30 and 31, and previous work on clusters, is shown in Figure 4.3.5.
111
Chapter Four
CH
CH3
H3C H 'C,
zi
Os Os
H—C—H
A
/ Os\
H,CH3
\çOscçCH
Figure 4.3.5: Stepwise formation of 1-methylallyl from 2-butyne
The proposed mechanism involves three main steps to change the ligand from
a 2-butyne to a I -methylallyl. The first step is the 2-butyne ligand bonding to an Os
atom in the cluster as a two electron donor, as in 31. A cluster hydride then transfers
to one of the alkyne carbons, breaking the triple bond. The ligand becomes it-bonded
to the Os atom, and a-bonds to an adjacent Os atom forming an edge bridging
alkylidene. This type of bonding mode is well known for alkynes, and is observed in
the Os cluster 0s3(CO)7(C6FL4)(PhCC(H)Ph)2 for the diphenylacetylene ligands, where
they have inserted into the bridging hydrides of the cluster. (2)
In this case the butyne then undergoes an internal hydrogen shift from the
terminal methyl group, breaking the bridging a-bond, and creating a 1-methylallyl
group. In the cluster 0s 3(CO)7(C6H4)(PhCC(H)Ph)2 there are no available hydrogens
to undergo a similar shift to create an allyl ligand.
The proposed mechanisms both seem possible explanations for the unexpected
formation of the 1-methylallyl ligand from 2-butyne, and the mechanism that
predominates depends upon species 31. This species is either the first step in the
112
Chapter Four
formation of the 1-methylallyl ligand, as in the second mechanism, or a separate
species, with the 2-butyne forming a 1-methylallyl ligand independently in one step.
113
Chapter Four
References
H. Chen, B.F.G. Johnson, J. Lewis, P.R. Raithby, I Organomet. Chem., 1991, 406, 219
H. Chen, B.F.G. Johnson, J. Lewis, P.R. Raithby, I. Organomet. Chem., 1989, 376, C7
M.R. Churchill, B.G. DeBoer, Inorg. Chem., 1977, 16, 878
H. Chen, B.F.G. Johnson, J. Lewis, Organometallics, 1989, 8, 2965.
M.A. Gallup, B.F.G. Johnson, J. Lewis, A.H. Wright, I. Chem. Soc., Dalton Trans., 1989, 481
J.A. Segal, B.F.G. Johnson, I Chem. Soc., Dalton Trans., 1975, 1990
T. Hosokawa, I. Moritani, S. Nishioka, Tetrahedron Lett., 1969, 3833
J.A. Bertrand, H.B. Jonassen, D.W. Moore, Jnorg. Chem., 1963, 2, 601
N.M. Boag, M. Green, J.L. Spencer, F.G.A. Stone, I Organomel. Chem., 1977, 127, C51
114
Chapter Five
Chapter Five
5 Experimental
5.1 General Experimental Procedures and Instrumentation
General
Trimethylamine-N-oxide dihydrate (Me 3NO.2H20), purchased from Aldrich,
was carefully dried by refluxing the sample (15g) in benzene (250 ml), typically
overnight, to remove the water of crystallisation via a Dean and Stark distillation. The
benzene was then decanted and the sample dried under vacuum on a Schienk line, and
sublimed prior to use. Addition of Me3NO to the reaction solutions was carried out
under an atmosphere of dry nitrogen, although no strict measurements were taken to
completely exclude air from the reaction systems.
Dichioromethane and diethyl ether were dried using CaH 2 and freshly distilled
prior to use. Acetonitrile was dried over 4A molecular sieves purchased from
Lancaster Chemicals. All other reagents were used as supplied without purification.
Osmium carbonyl was purchased from Oxkem Ltd. and all other reagents were
purchased from Aldrich or Lancaster Chemicals.
Seperations
All separations were achieved chromatographically on silica, on the open
bench without any precautions to exclude air. Thin layer chromatography (tic) was
carried out using glass plates (20 cm x 20 cm) coated with a 0.25 cm layer of silica
115
Chapter Five
gel 60 F254, which were supplied by Merck. Column chromatography was carried out
using a 50 cm long glass column with an internal diameter of 3 cm, fitted with a 100
ml solvent reservoir, and a facility for pressurisation. The column was packed with 60
mesh silica and the eluants used for both column and thin layer chromatography were
mixed from standard grade laboratory solvents.
Crysiallisations
Single crystals of high quality were required for the collection of X-ray
diffraction data and were typically grown from pentane solutions at low temperature,
unless otherwise stated.
Infra-red Spectroscopy
Infra-red spectra were recorded in dichloromethane in NaCl cells (0.5 mm
path length) supplied by Specac Ltd., using a Perkin-Elmer Series 1600 fourier
transform instrument.
Mass Spectrometry
Fast atom bombardment mass spectra were obtained on a Kratos MS50TC
spectrometer which was run in positive mode. Samples were run in a matrix of 3-
NOBA (meta-nitrobenzyl alcohol).
116
Chapter Five
AMR Spectroscopy
'H NIvIIR spectra were recorded on Bruker WH 200 or 250 MHz fourier
transform instruments. All spectra described herein were recorded in deuterated
solvents and were referenced to an internal trimethylsilane (TMS) standard.
Single Crystal X-ray Diffraction Studies
Diffraction data were collected on a Stoe Stadi 4-circle diffiactometer. An
Oxford Cryosystems device was used for low temprature data collection.' The
appropriate crystal data, data collection and structural refinement parameters are
presented in the text, and full crystallographic listings are given in the appendices. All
refinements were carried out using the crystallographic program SHELXL 93, (2) and
all figures were produced using SHELXTL PC. 3 When metal hydrides could not be
located by direct experiment they were positioned using the program XHYDEX. 4
This program employs a potential energy technique in order to define the most likely
site for a hydride ligand to adopt in a cluster. Optimum positions are found for each
postulated hydride site by minimisation of the potential energy of the intramolecular
non-bonded interactions involving the hydride. The resultant potential energy enables
a quantitative comparison to be made of the various possible hydride locations on the
cluster.
117
Chapter Five
5.2 Experimental Details for Chapter Two
Preparation of ('t7neda,)Pd'Cl,.)2 (5)
Palladium chloride (0.9895g, 5.55mmol) was dissolved in acetonitrile (50 ml)
and was heated at reflux for lh. The solution was allowed to cool to room
temperature and a pale yellow suspension formed. A slight excess of tmeda (1.20 ml,
1.5 mol. equiv.) was added, and the suspension immediately turned bright yellow in
colour. The precipitate was filtered off, and washed three times with diethyl ether (3 x
15 ml). The resultant yellow solid was dried under vacuum. (Yield 84%)
Preparation of (t,neda)Pd(Me)2 (5)
The compound (tmeda)Pd(Cl) 2 (1 .3624g, 4.63 mmol)) was suspended in diethyl
ether (30 ml) and cooled to -30 °C using an acetone/CO2 bath. A slight excess of
MeLi (7.5 ml, 2.5 mol. equiv.) was added with stirring. The solution was allowed to
warm to 0 °C and was stirred for a further lh. Ice cold water (10 ml) was added until
a clear organic layer and a black water layer had formed. The organic layer was
seperated and dried over MgSO 4, before the solvent was removed under reduced
pressure leaving a white precipitate. (Yield 77%)
Preparation of (tmeda)Pd(Me) (7) (5)
The compound (tmeda)Pd(Me)2 (0.3565g, 1 .4Ommol)) was dissolved in
benzene (10 ml) before the addition of Mel (0.12 ml, 1.1 mol. equiv.). A brown
precipitate was formed, which was filtered and dried at reduced pressure. (Yield 91%)
118
Chapter Five
Preparation of (rmeda)Pd(COMe) (6)
The compound (tmeda)Pd(Me)(I) (0.5549g, 1 .52mmol)) was dissolved in
chloroform (5 ml) and a slow stream of CO gas was bubbled through the solution for
the period of im. The solution immediately turned pale brown and was left to stir for
I under a CO atmosphere. The solution was then reduced in volume to 1 cm' under
vacuum, and pentane (10 ml) was added. A light brown precipitate appeared which
was filtered off and dried at reduced pressure. (Yield 64%)
Preparation of (bpy)Pd(COMe) (I) (7)
The compound (tmeda)Pd(COMe)(I) (0.55g, 1 .4Ommol) was dissolved in
dichloromethane (50 ml) and the solution was cooled to 0 T. An excess of 2-2'
dipyridyl (bpy) (0.7168g, 3 mol. equiv.) was added and the solution was stirred at 0
°C for 18h. The solvent was removed at reduced pressure and the resultant orange
solid was washed with diethyl ether (2 x 20 ml). The compound was finally dried at
reduced pressure. (Yield 96%)
Synthesis of {(bpy)Pd(Cd -Ii 000Me)} (OTj)
The compound (bpy)Pd(COMe)(I) (46mg, 0.1 lmmol) was dissolved in
dichloromethane (40 ml) and the solution was cooled to 0 T. To the solution was
added acetonitrile (2 ml), cyclohexene (0.016 ml, 1.5 mol. equiv.) and silver triflate
(41mg). A white solid immediately separated and the solution was allowed to stir at 0
°C for a further 3h. The solution was filtered and the solvent was removed under
reduced pressure. The resultant residue was washed with diethyl ether (2 x 40 ml) to
remove any residual acetonitnle and dried under vacuum. (Yield 12%)
119
Chapter Five
Spectroscopic data for {(bpy)Pd(C 6H1000Me)}(OTf): IR v(COCH3) 1690(m); MS: M4 = 387(calc.
387) amu
Synthesis of {(bpy)Pd(C 6H8COMe)} (OTJ)- (1,3)
The compound (bpy)Pd(COMe)(I) (45mg, O.lOmmol) was dissolved in
dichloromethane (40 ml) and the solution was cooled to 0 T. To the solution was
added acetonitrile (1.5 ml), 1,3 cyclohexadiene (0.015 ml, 1.5 mol. equiv.) and silver
trifiate (41mg). A white solid immediately separated and the solution was allowed to
stir at 0 °C for a further 3h. The solution was filtered and the solvent was removed
under reduced pressure. The resultant residue was washed with diethyl ether (2 x 40
ml) to remove any residual acetonitrile and dried under vacuum. (Yield 10%)
Spectroscopic data for {(bpy)Pd(C 6H3COMe))(OTf): IR v(COCH3) 1682 (m); MS: M = 385 (caic.
385) amu
Synthesis of {(bpy)Pd(C61LCOMe)} (OTj)- (1,4)
The compound (bpy)Pd(COMe)(I) (100mg, 0.23mmol) was dissolved in
dichloromethane (40 ml) and the solution was cooled to 0 T. To the solution was
added acetonitrile (1.5 ml), 1,4 cyclohexadiene (0.028 ml, 1.5 mol. equiv.) and silver
trifiate (96mg). A white solid immediately separated and the solution was allowed to
stir at 0 °C for a further 3h. The solution was filtered and the solvent was removed
under reduced pressure. The resultant residue was washed with diethyl ether (2 x 40
ml) to remove any residual acetonitrile and dried under vacuum. (Yield 12%)
Spectroscopic data for {(bpy)Pd(C 6H8COMe)}(OTf): IR v(COCH 3) 1656 (m); MS: M = 385 (caic.
385) amu
120
Chapter Five
Synthesis of {(bpy)Pd(C 8H12COMe)} (OTj)
The compound (bpy)Pd(COMe)(I) (43mg, 0. lOmmol) was dissolved in
dichloromethane (40 ml) and the solution was cooled to 0 T. To the solution was
added acetonitrile (1.5 ml), cyclooctadiene (0.020 ml, 1.5 mol. equiv.) and silver
triflate (41mg). A white solid immediately separated and the solution was allowed to
stir at 0 °C for a further 3h. The solution was filtered and the solvent was removed
under reduced pressure. The resultant residue was washed with diethyl ether (2 x 40
ml) to remove any residual acetonitrile and dried under vacuum. (Yield 12%)
Spectroscopic data for {(bpy)Pd(C 8H12COMe)}(OTf): IR v(COCH3) 1654 (m); MS: M = 413 (caic.
413) amu
Attempted Synthesis of {(bpy)Pd(C6 -I6COMe)} (0 Tj)
The compound (bpy)Pd(COMe)(I) (55mg, 0.13mmol) was dissolved in
dichloromethane (40 ml) and the solution was cooled to 0 T. To the solution was
added acetonitrile (2 ml), benzene (0.020 ml, 1.5 mol. equiv.) and silver triflate
(5 0mg). A white solid immediately separated and the solution was allowed to stir at 0
°C for a further 3h. The solution was filtered and the solvent was removed under
reduced pressure. The resultant residue was washed with diethyl ether (2 x 40 ml) to
remove any residual acetonitrile and dried under vacuum.
Attempted Synthesis of ((bpy)Pd(C 6Hs(F)COMe)} (07'))
The compound (bpy)Pd(COMe)(I) (45mg, 0.10mmol) was dissolved in
dichioromethane (40 ml) and the solution was cooled to 0 °C. To the solution was
added acetonitrile (1.5 ml), fluorobenzene (0.017 ml, 1.5 mol, equiv.) and silver
triflate (4 1mg). A white solid immediately separated and the solution was allowed to
121
Chapter Five
stir at 0 °C for a further 3h. The solution was filtered and the solvent was removed
under reduced pressure. The resultant residue was washed with diethyl ether (2 x 40
ml) to remove any residual acetonitrile and dried under vacuum.
Attempted Synthesis of ((bpy)Pd(C 6J-15(Br)COMe)} (OTJ)
The compound (bpy)Pd(COMe)(I) (45mg, O.lOmmol) was dissolved in
dichloromethane (40 ml) and the solution was cooled to 0 °C. To the solution was
added' acetonitrile (1.5 ml), bromobenzene (0.017 ml, 1.5 mol. equiv.) and silver
triflate (41mg). A white solid immediately separated and the solution was allowed to
stir at 0 °C for a further 3h. The solution was filtered and the solvent was removed
under reduced pressure. The resultant residue was washed with diethyl ether (2 x 40
ml) to remove any residual acetonitrile and dried under vacuum.
Attempted Synthesis of {(bpy)Pd(C 8H8COMe)} (OTJ)
The compound (bpy)Pd(COMe)(I) (46mg, 0.1 Immol) was dissolved in
dichioromethane (40 ml) and the solution was cooled to 0 T. To the solution was
added acetonitrile (1.5 ml), cyclooctatetraene (0.018 ml, 1.5 mol. equiv.) and silver
triflate (42mg). .A white solid immediately separated and the solution was allowed to
stir at 0 °C for a further 3h. The solution was filtered and the solvent was removed
under reduced pressure. The resultant residue was washed with diethyl ether (2 x 40
ml) to remove any residual acetonitrile and dried under vacuum.
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Chapter Five
Attempted Synthesis of {(bpy)Pd(C6H5(Me)COMe)} (OTj)
The compound (bpy)Pd(COMe)(I) (48mg, 0.1 immol) was dissolved in
dichloromethane (40 ml) and the solution was cooled to 0 T. To the solution was
added acetonitrile (1.5 ml), toluene (0.018 ml, 1.5 mol. equiv.) and silver trifiate
(43mg). A white solid immediately separated and the solution was allowed to stir at 0
°C for a further 3h. The solution was filtered and the solvent was removed under
reduced pressure. The resultant residue was washed with diethyl ether (2 x 40 ml) to
remove any residual acetonitrile and dried under vacuum.
Attempted Synthesis of {(bpy)Pd(C6 -14(OH)2COMe)} (OTj)
The compound (bpy)Pd(COMe)(I) (41mg, 0.09mmol) was dissolved in
dichloromethane (40 ml) and the solution was cooled to 0 °C. To the solution was
added acetonitrile (1.5 ml), hydroquinone (17mg, 1.5 mol. equiv.) and silver trifiate
(40mg). A white solid immediately separated and the solution was allowed to stir at 0
°C for a further 3h. The solution was filtered and the solvent was removed under
reduced pressure. The resultant residue was washed with diethyl ether (2 x 40 ml) to
remove any residual acetonitrile and dried under vacuum.
Attempted Synthesis of (tmeda)Pd(Ph) 2
The compound (tmeda)PdC12 (120mg, 0.41mmol) was suspended in diethyl
ether (30 ml) and cooled to -30T using an acetone/CO2 bath. A slight excess of PhLi
(0.5 ml, 1.5 mol. equiv.) was added with stirring. The solution was allowed to warm
to 0°C and was stirred for a further lh. Ice cold water (10 ml) was added until a clear
organic layer was separated and dried over MgSO 4 . The solvent was removed under
reduced pressure.
123
Chapter Five
Spectroscopic data: 'H NIvIR (CDCI 3): 6 2.54 (s, 2 x -N(CH3)2), 2.26 (s, 2 x -CH2-)
5.3 Experimental Details for Chapter Three
Preparation of 0s3(CO) jo(NCMe) 2
0s3(CO) 1 2 (0.5021g, 0.55mmol) was dissolved in a solution of
dichloromethane (200 ml) and acetonitrile (50 ml). A solution of Me 3NO (0.1052g.
2.5 mol. equiv.) in acetonitrile (100 ml) was added dropwise over 3h and the resultant
solution was allowed to stir for a further lh. The solution was then filtered through
silica to remove any unreacted starting material and the solvent was then removed
under reduced pressure.
Synthesis of 0s 3(CO) 9(H)2(C6H3F)
The compound 0s 3(C0) 1o(NCMe) 2 (0.5243g, 0.56mmol) was dissolved in
flourobenzene (50 ml) and was heated at reflux for lh. The solution was allowed to
cool to room temperature before being filtered through silica. The solvent was
removed under reduced pressure followed by product seperation by tic using hexane
as eluant. One major band was produced as well as two minor bands and cluster
decomposition. These were extracted into dichloromethane and characterised
spectroscopically as 0s 3(CO) 1 2 12 (yellow), 0s3(C0) 10(NCMe)2 13 (yellow), and
0s3(CO)9(H')2(C6H3F) 14 (yellow, 20 %). Single crystals of 14 suitable for X-ray
diffraction analysis were grown.
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Chapter Five
Spectroscopic data for 0s 3(CO)9(H')2(C6H3F): IR (CH 202): v(CO) 2114 (m), 2083 (s), 2056 (s), 2035
(m), 2021 (m), 2007 (m), 2000 (sh) cm -'; 'H NMR (CDC1 3): 8 7.65 (d, J= 7.82 Hz, 1H), 6.95 (m, J
5.82 Hz, 1H), 6.58 (t, J= 7.74 Hz, 1H), -18.3 (s, 2H) ppm; MS: M= 920 (caic. 918) amu
Crystal measurement and details for 0s 3(CO) 9(H)2(C6H3F): Formula C 15H5F090s3, M.Wt. 918.79
amu, crystal size/mm 0.36 x 0.32 x 0.24, crystal system Monoclinic, space group P2(1)/c, a=
9.4776(8) A, b= 10.429(2) A, c= 20.023(2) A, oL= 90 0 3= 98.578(8) o . 90 0 Volume= 1957.0(4)
A, Z= 4, F(000) 1616, Pcaic= 3.118 Mgm 3 , ? (Mo-K,,,)= 0.71073 A, temperature 293(2) K, 20
range= 2.06 to 30.00 0 measured reflections 7334, unique observed reflections [1>2a(I)1 5713, No.
of refined parameters 259, goodness of fit on F 1.015, final R indices R [I>2c(I)J R1 0.0546,
wR2= 0. 1092, R indices (all data) R1= 0. 1073, wR2= 0.1333
Synthesis of 0s 3(CO) 9(H)2(CJI3C1)
The compound 0s3(CO) io(NCMe)2 (0.8205g. 0.88mmol) was dissolved in
chlorobenzene (50 ml) and was heated at reflux for lh. The solution was allowed to
cool to room temperature before being filtered through silica. The solvent was
removed under reduced pressure followed by product seperation by tic using hexane
as eluant. One major band was produced as well as two minor, bands and cluster
decomposition. These were extracted into dichioromethane and characterised
spectroscopically as 0s 3(CO) 12 12 (yellow), 0s3(CO) io(NCMe)2 13 (yellow), and
0s3(CO)9(H)2(C6H3C1) 15 (yellow, 22%). Single crystals of 15 suitable for X-ray
diffraction analysis were grown.
Spectroscopic data for 0s 3(CO)9(H)2(C6H3C1): JR (CH 202): v(CO) 2110 (m), 2083 (s), 2058 (s),
2037 (m), 2025 (m), 2011(m), 2003(sh), 1987 (m) cm'; 'H NMR (CDC1 3): 8 7.89 (d, J= 8.4 Hz,
1H), 7.83 (d, J= 7.8 Hz, 1H), 7.30 (d, J= 7.3 Hz, IH), 6.82 (t, J= 7.5 Hz, 11-I'), -18.7 (s, 2H); MS: M=
936 (calc. 934) ainu
Crystal measurement and details for 0s 3(CO)9(H)2(C6H3C1): Formula C 15H50090s3 , M.Wt. 935.24
amu, crystal size/nun 0.39 x 0.27 x 0.21, crystal system Triclinic, space group P-i, a= 8.666(5) A,
b= 9.309(5) A, c= 14.107(8) A, a= 100.04(3) 0 P= 97.27(2) 0 116.83(3) 0 Volume 972.3(9)
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Chapter Five
A, Z= 2, F(000)= 824, p = 3.194 Mgm 3 , ? (Mo-K,)= 0.71073 A, temperature 150(2) K, 20
range= 2.54 to 25.06 0 measured reflections 3469, unique observed reflections [I>2c(I)] 3444, No.
of refined parameters 255, goodness of fit on F 1.027, conventional R [F>4c(F)] Ri- 0.0502, wR2=
0.0883, R indices (all data) R1=0.0242, wR2= 0.0860.
Attempted Synthesis of 0s3(CO)9(H)2(Cdl3Br)
The compound 0s3(CO) io(NCMe)2 (0.5673g, 0.61mmol) was dissolved in
bromobenzene (50 ml) and was heated at reflux for lh. The solution was allowed to
cool to room temperature before being filtered through silica. The solvent was
removed under reduced pressure followed by product seperation by tic using hexane
as eluant. One major band was produced as well as two minor bands and cluster
decomposition. These were extracted into dichloromethane and characterised
spectroscopically as 0s3(CO) 12 12 (yellow), 0s3(CO) 10(NCMe)2 13 (yellow), and
0s3(C0) 1o(jt-Br)2 16 (orange, 15%). Single crystals of 16 suitable for X-ray
diffraction analysis were grown.
Spectroscopic data for 0s 3(C0)9(H)2(C6H3Br): IR (CH202): 2113 (m), 2082 (s), 2053 (s), 2014 (w),
2007 (s), 1998 (sh) cm; 1H NUR (CDC1 3): signal oscured by unreacted bromobenzene; MS: M=
1012 (calc. 984) amu
Synthesis of Os 3(CO)9(H)2(C5J-L31vIe)
The compound 0s3(CO) jo(NCMe)2 (0.5998g. 0.64mmol) was dissolved in
toluene (50 ml) and was heated at refiux for lh. The solution was allowed to cool to
room temperature before being filtered through silica. The solvent was removed under
reduced pressure followed by product seperation by tic using hexane as eluant. One
major band was produced as well as two minor bands and cluster decomposition.
These were extracted into dichloromethane and characterised spectroscopically as
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Chapter Five
0s3(CO)12 12 (yellow), 0s3(CO)io(NCMe)2 13 (yellow), and 0s3(CO)9(H)2(C6H3Me)
17 (yellow,24%). Single crystals of 17 suitable for X-ray diffraction analysis were
grown.
Spectroscopic data for 0s 3(CO) 9(H) 2(C6H3Me): IR (CH2C1 2): 2109 (m), 2079 (s), 2052 (s), 2033 (s),
2022 (w), 2002 (s), 1997 (sh) cm'; 'H NMR (CDC1 3): 8 7.84 (d, J= 8.3 Hz, 111), 7.74 (d, J= 8.3 Hz,
111), 7.71 (s, 111), 6.73 (m, 1H), 6.73 (dd, J= 8.3 Hz, 1H), 2.45 (s, 3H), 2.31 (s, 314), -18.5 (s, 2H);
MS: M 4 = 918 (calc. 914) amu
Crystal measurement and details for 0s 3 (CO)9(H)2(C6H3Me): Formula C, 6H8O9Os3 , M.Wt. 914.82
amu, crystal size/nun 0.43 x 0.23 x 0.19, crystal system Triclinic, space group P-i, a= 9.260(2) A,
b= 13.115(2) A, c= 16.633(3) A, a= 91.01(2) 0, 3= 93 . 58(2) 0, y= 92 . 23(2) 0 , Volume 2014.1(6)
A, Z= 4, F(000) 1616, Pcalc= 3.017 Mgm 3 , ?. (Mo-K)= 0.71073 A, temperature 150(2) K, 20
range= 2.59 to 27.53 0 measured reflections 9479, unique observed reflections [1>2(I)] 9234, No.
of refined parameters 505, goodness of fit on F 1.008, final refinement factor indices (R) [I>2c(I)]
R1= 0.0503, wR2= 0. 1215, R indices (all data) R1= 0.0786, wR2= 0.1358.
Synthesis of 0s 3(C0) 9(H) 2 {0rth0-C6 12(Me)2}
The compound 0s3(CO) jo(NCMe)2 (0.5746g, 0.62mmol) was dissolved in
ortho-xylene (50 ml) and was heated at reflux for lh. The solution was allowed to
cool to room temperature before being filtered through silica. The solvent was
removed under reduced pressure followed by product seperation by tic using hexane
as eluant. One major band was produced as well as two minor bands and cluster
decomposition. These were extracted into dichloromethane and characterised
spectroscopically as 0s3(CO)12 12 (yellow), 0s 3(CO) jo(NCMe)2 13 (yellow), and
0s3(CO)9(H)2 [ortho-C6H2(Me)2] 18 (yellow, 23%). Single crystals of 18 suitable for
X-ray diffraction analysis were grown.
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Chapter Five
Spectroscopic data for 0s3(CO)9(H) 2 {ortho-C 6H2(Me)2}: IR (CH202) v(CO) 2107 (m), 2079 (s),
2053 (s), 2033 (s), 2022 (m), 2006 (s), 1997 (m), 1981 (m) cm'; 'H NTvIR (CDC1 3): S 7.60 (s, 2H),
2.19 (s, 611), -18.1 (s, 2H); MS: M= 930 (caic. 928) amu
Crystal measurement and details for 0s 3(CO)9(H)2(C6H3(Me)2): Formula C 17H, 0090s3
M.Wt. 928.85 arnu, crystal size/mm 0.23 x 0.16 x 0.06, crystal system Triclinic, space group P-i, a=
8.873(11) A, b= 9.708(8) A, c= 13.664(12) A, cx= 79.95(7) 0 = 73.56(8) 0 y= 64.88(8) 0
Volume= 1019(2) A, Z= 2, F(000) 824, Pcalc= 3.028 Mgm 3 , ? (MOKa)= 0.71073 A, temperature
150(2) K, 20 range= 2.61 to 22.48 0 measured reflections 2341, unique observed reflections
[1>2(I)] 2333, No. of refined parameters 179, goodness of fit on P 1.016, conventional R [F>4c(F)]
R1= 0.045 1, R indices (all data) R1= 0.0660, wR2= 0.1143.
Synthesis of 0s 3(CO)p(H)2(meta-Cd-12(Me)2)
The compound 0s3 (C0),o(NCMe)2 (0.5243g, 0.56mmol) was dissolved in
meta-xylene (50 ml) and was heated at reflux for lh. The solution was allowed to
cool to room temperature before being filtered through silica. The solvent was
removed under reduced pressure followed by product seperation by tic using hexane
as eluant. One major band was produced as well as two minor bands and cluster
decomposition. These were extracted into dichioromethane and characterised
spectroscopically as 0s 3(CO) 12 12 (yellow), Os3(C0) 1o(NCMe)2 13 (yellow), and
0s3(C0)9(H)2[meta-C6H2(Me)2] 19 (yellow, 21%). Single crystals of 19 suitable for
X-ray diffraction analysis were grown.
Spectroscopic data for 0s3(C0)9(H)2{meta-C 6H2(Me)2 }: JR (CH202) v(CO) 2105 (m), 2076 (s),
2052 (s), 2032 (s), 2021 (m), 2005 (m), 1997 (sh) cm'; 'H NMR (CDC1 3): 8 7.43 (s, 1H), 6.80 (s,
IH), 2.19 (s, 311), 2.17 (s, 3H), -18.X (s, 2H); MS: M= 932 (calc. 928) amu
Crystal measurement and details for 0s 3(C0)9(H)2(C6H3(Me)2): Formula C171-11009Os3
M.Wt. 928.85 arnu, crystal size/nun 0.25 x 0.16 x 0. 16, crystal system Triclinic, space group P-i, a=
8.257(3) A, b 9.114(4) A, c= 14.771(6) A, a= 90.70(3) 0 P= 100.92(4) 0 y= 109.80(3) 0
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Chapter Five
Volume= 1023.4(7) A, Z= 2, F(000) 824, Pcaic 3.014 Mgm 3 , X (Mo-K)= 0.71073 A,
temperature 150(2) K, 20 range= 2.67 to 30.07 0 measured reflections 6781, unique observed
reflections [I>2c(I)] 5984, No. of refined parameters 265, goodness of fit on P 0.999, conventional
R [F>4cy(F)] R1= 0.0442, R indices (all data) R1 0.0660, wR2= 0.1097.
Attempted synthesis of 0s 3(CO) 9(H)2 {para-C6H2(Me) 2}
The compound 0s3(CO) io(NCMe)2 (0.5548g, 0.59mmol) was dissolved in
para-xyiene (50 ml) and was heated at refiux for lh. The solution was allowed to cool
to room temperature before being filtered through silica. The solvent was removed
under reduced pressure followed by product seperation by tic using hexane as eluent.
Two major bands and cluster decomposition. These were extracted into
dichloromethane and characterised spectroscopically as 0s 3(CO) jo(NCMe)2 13
(yellow), and 0s 3(CO) 1 2 12 (yellow).
Reaction of 0s 3(CO) j o(NCMe) 2 and a-methylstyrene
The compound 0s 3(CO) jo(NCMe)2 (0.5126g, 0.55mmol) and cc-methylstyrene
(2-3 cm3 excess) were dissolved in octane (50 ml) and the mixture was heated at
reflux for 3h. The solution was allowed to cool to room temperature before being
filtered through silica. The solvent was removed under reduced pressure followed by
product seperation by tic using hexane as eluant. Four major bands were produced,
and these were extracted into dichloromethane and characterised spectroscopically as
0s3(CO)12 1 (yellow), 0s 3(CO) 1o(NCMe)2 2 (yellow), 0s3(CO)9(H)2
(C6H3(C(CH3)CH2)} 21 (yellow, 6%), and 0s3(CO)9(H)2 {C6H3(C(CH3)CH2)} 22
(yellow, 5%),
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Chapter Five
Spectroscopic data for 21: JR v(CO) 2122 (w), 2100 (w), 2080 (s), 2064 (m), 2054 (s), 2037 (m),
2020 (m), 2008 (sh), 1999 (w) cm; MS: M= 941 (calc. 939) amu
Spectroscopic data for 22: JR v(CO) 2122 (w), 2077 (sh), 2065 (s), 2050 (m), 2039 (m), 2023 (m),
2016 (m), 2006 (sh); MS: M= 941 (calc. 939) amu
Reaction of 0s 3(CO) j o(NCMe) 2 and styrene
The compound 0s3(CO) 1o(NCMe)2 (0.5109g. 0.55mmoi) and styrene (2-3
cm excess) were dissolved in octane (50 ml) and was heated at refiux for 3h. The
solution was allowed to cool to room temperature before being filtered through silica.
The solvent was removed under reduced pressure followed by product seperation by
tic using hexane as eluant. Three major bands were produced, and these were
extracted into dichloromethane and characterised spectroscopically as 0s 3(CO) 1 2 12
(yellow), 0s3(CO)io(NCMe)2 13 (yellow), and 0s3(CO)9(H)2 {C6H3(CHCH2)} 23
(yellow, 10%).
Spectroscopic data for 0s3 (CO)9(H)2 {C6H3(CHCH2)): JR (CH202): v(CO) 2120 (w), 2079 (s), 2064
(s), 2054 (in), 2037 (m), 2021 (m), 2007 (m) cm -1 ; 1 H NMR (CDC1 3): sample to weak to asssign
MS: M 4 = 926 (calc. 926) amu
Reaction of 0s 3(CO) 1o(NCMe) 2 and 1,3 diisopropenylbenzene
The compound 0s3(CO) io(NCMe)2 (0.4982g, 0.53mmol) and 1,3
diisopropenylben.zene (2-3 cm 3 excess) were dissolved in octane (50 ml) and was
heated at reflux for 3h. The solution was allowed to cool to room temperature before
being filtered through silica. The solvent was removed under reduced pressure
followed by product seperation by tic using hexane as eluant. Two major bands were
130
Chapter Five
produced, and, these were extracted into dichioromethane and characterised
spectroscopically as 0s 3(CO) 12 12 (yellow) and 0s 3(CO) 10(NCMe)2 13 (yellow).
5.4 Experimental Details for Chapter Four
Synthesis of 0s 3(C0) 9(I-I)2 (C6H2(F) (COMe))
Aluminium trichloride (90mg, 0.67mmol) and acetyl chloride (3.3 ml) were
dissolved in carbon disulfide (20 ml) and the solution was cooled to 0 T. A solution
Of 0s3(CO)9(H)2(C6H3F) (45mg, 0.05mmol) in carbon disulfide (15 ml) was added
dropwise over lh. The resultant solution was allowed to warm to room temperature
over a further lh, before being filtered through silica. The solvent was removed under
reduced pressure followed by product seperation by tic using hexane-dichioromethane
(1:1 v/v) as eluant. One major band was produced as well as some cluster
decomposition. The major band was extracted into dichloromethane and characterised
spectroscopically as 0s 3(CO)9(H)2 { C6H2(F)(COMe) } 25 (yellow, 10%).
Spectroscopic data for 0s 3(CO)9(H)2 {C6H2(F)(COMe)}: JR v(CO) 2116 (m), 2085 (s), 2058 (s), 2038
(s), 2024 (m), 2010 (m), 2002 (w) cm'; MS: M"= 960 (960) ainu
Synthesis of 0s 3(CO)p(H) 2 (C6F12(Cl)(COMe))
Aluminium trichloride (110mg, 0.82mmol) and acetyl chloride (4.0ml) were
dissolved in carbon disulfide (20 ml) and the solution was cooled to 0 T. A solution
Of 0s3(CO)9(H)2(C6H3C1) (55mg, 0.06mmol) in carbon disulfide (15 ml) was added
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Chapter Five
dropwise over lh. The resultant solution was allowed to warm to room temperature
over a further lh, before being filtered through silica. The solvent was removed under
reduced pressure followed by product seperation by tic using hexane-dichioromethane
(1:1 v/v) as eluant. One major band was produced as well as some cluster
decomposition. The major band was extracted into dichloromethane and characterised
spectroscopically as 0s3(CO)9(H)2 { C6H2(Cl)(COMe) } 26 (yellow, 7%)
Specroscopic data for 0s 3(CO)9(H)2 {C6H3(C1)(COMe)}: IR v(CO) 2112 (m), 2085(s), 2059 (s), 2039
(m), 2028 (s), 2014 (m), 2006 (m) cm'; MS: M= 978 (caic. 976)
Synthesis of 0s 3(CO)p(H) 2 (C6112(Me) (COMe)]
Aluminium trichloride (134mg, 1.01mmol) and acetyl chloride (4.7 ml) were
dissolved in carbon disulfide (20 ml) and the solution was cooled to 0 T. A solution
of 0s3(CO)9(H)2(C6H3Me) (67mg, 0.07mmol) in carbon disulfide (20 ml) was added
dropwise over lh. The resultant solution was allowed to warm to room temperature
over a further 1 h, before being filtered through silica. The solvent was removed under
reduced pressure followed by product seperation by tic using hexane-dichloromethane
(1:1 v/v) as eluant. One major band was produced as well as some cluster
decomposition. The major band was extracted into dichloromethane and characterised
spectroscopically as 0s3(CO)9(H)2 { C6H2(Me)(COMe) } 27 (yellow, 10%).
Spectroscopic data for 0s 3(CO)9(H)2 (C6H3(Me)(COMe)}: IR v(CO) 2113 (m), 2082 (s), 2054 (s),
2035 (m), 2025 (m), 2006 (m) cm'; MS: M += 954 (caic. 956)
Synthesis of 0s3(CO)9(H)2{Cd -I(Me)2(COMe)}
Aluminium trichloride (178mg, 1 .33mmol) and acetyl chloride (6.2th1) were
dissolved in carbon disulfide (20 ml) and the solution was cooled to 0 T. A solution
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Chapter Five
Of 0s3 (C0)9(H)2 [oriho-C 6H2(Me)21 (89mg, 0.09mmol) in carbon disulfide (20 ml)
was added dropwise over lh. The resultant solution was allowed to warm to room
temperature over a further lh, before being filtered through silica. The solvent was
removed under reduced pressure followed by product seperation by tic using hexane-
dichloromethane (1:1 v/v) as eluant. One major band was produced as well as some
cluster decomposition. The major band was extracted into dichloromethane and
characterised spectroscopically as 0s 3(CO)9(H)2 (C6H(Me)2(COMe)) 28 (yellow,
6%).
Spectroscopic data for 0s 3(C0)9(H)2 { C6H(Me)2(COMe) }: JR v(CO) 2110 (m), 2082 (s), 2054 (s),
2036 (s), 2024 (m), 2008 (m) cm'; MS: M += 975 (calc. 970) amu
Synthesis of 0s 3(C0)p(H)2(C6H(Me) 2(C0Me)}
Aluminium trichioride (122mg, 0.91mmøl) and acetyl chloride (4.5 ml) were
dissolved in carbon disulfide (20 ml) and the solution was cooled to 0 °C. A solution
Of 0s3(CO)9(H)2[meia-C6H2(Me)2] (61mg, 0.06mmol) in carbon disulfide (20 ml) was
added dropwise over lh. The resultant solution was allowed to warm to room
temperature over a further lh, before being filtered through silica. The solvent was
removed under reduced pressure followed by product seperation by tic using hexane-
dichloromethane (1:1 v/v) as eluant. One major band was produced as well as some
cluster decomposition. The major band was extracted into dichioromethane and
characterised spectroscopically as 0s 3(CO)9(H)2 {C6H(Me)2(COMe) } 29 (yellow,
5%).
Spectroscopic data for 0s 3(C0)9(H)2 { C6H(Me)2(COMe) }: JR v(CO) 2108 (m), 2078 (s), 2054 (s),
2033 (m), 2023 (m), 2008 (m) cm'; MS: M += 972 (caic. 970) aniu
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Chapter Five
Reaction of 0s 3(CO) 9(H)2('C61-13F) and 2-butyne
The compound 0s 3(CO)9(H)2(C6H3F) (42mg, 0.05mmol) and 2-butyne (2-3
drops excess) were dissolved in dichioromethane (50 ml). A solution of Me 3NO
(7mg, 2.2 mol. equiv.) in dichioromethane was added dropwise over lh. The resultant
solution was filtered through silica and the solvent was removed at reduced pressure.
The product was dissolved in dichloromethane and seperated by tic using hexane as
eluant. Two major bands were produced which were extracted into dichioromethane
and characterised spectroscopically as 0s 3 (CO)s(H)(CH2CHCHCH3)(C6H3F) 30 and
31 (yellow, 12% and 10%).
IR 30 v(CO) 2080 (m), 2049 (s), 2029 (m), 2000 (m), 1983 (w) cm -1 ; MS: M+= 945 (calc. 945)
JR 31 v(CO) 2081 (m), 2057 (sh), 2047 (s), 2029 (s), 1992 (m) cm'; MS: M += 953 (calc. 945)
Crystal measurement and details for 0s 3(CO)8(H)(CH2CHCHCH3)(C6H3F) 30: Formula C 1 8H11 080s3
M.Wt. 944.87 ainu, crystal size/mm 0.25 x 0.16 x 0. 16, crystal system Monoclinic, space group P-
2(1)/n, a= 15.131(5) A, b= 18.430(6) A, c= 15.297(5) A, 90 0 f3= 101.36(4) 0 -y= 90 0
Volume= 4182(2) A, Z= 8, F(000) 3360, pclr= 3.001 Mgm , ? (Mo-K)= 0.71073 A,
temperature 220(2) K, 20 range= 2.59 to 25.03 O measured reflections 9283, unique observed
reflections [I>2cr(I)] 7369, No. of refined parameters 553, goodness of fit on F 1.041, conventional
R [F>4(F)] R1= 0.0643, R indices (all data) R1 0.1356, wR2= 0. 1442.
134
Chapter Five
5.5 References
J. Cosier, A.M. Glaser, J. Appi. Crytallogr., 1986, 19, 105
G.M. Sheidrick, SHELXL 93, Program for crystal structural refinement, University of Gottingen, Germany, 1993
G.M. Sheidrick, SHELXTL PC, University of Gottingen and Siemens Analytical X-ray Instruments, Madison, 1990
A.G. Orpen, XHYDEX, Program for locating hydrides, Bristol University, 1980 see also: A.G. Orpen, J. Chem. Soc., Dalton Trans., 1980, 2509
W. de Graaf, J. Boersma, W.J.J. Smeets, A.L. Spek, G. van Koten, Organometallics, 1989, 8, 2907
W. de Graaf, J. Boersma, G. van Koten, Organometallics, 1990, 9, 1479
B.A. Markies, M.H.P. Rietveld, J. Boersma, A.L. Spek, G. van Koten, .1. Organomet. Chem., 1992, 424, Cl 2
135
0s3(CO)t-H)2(C6R31F)
Table 1. Crystal data and structure refinement for 0s3(C0)9(H)2(C6113})
Identification code si021
Empirical formula C15 H5 F 09 0s3
Formula weight 918.79
Temperature 293(2) K
Wavelength 0.71073 A Crystal system Monoclinic
Space group P2(1)/c
Unit cell dimensions a = 9.4776(8) A alpha =90 deg.
b = 10.429(2) A beta = 98.578(8) deg.
c = 20.023(2) A gamma =90 deg
Volume 1957.0(4) A Z 4
Density (calculated) 3.118 Mg/m'3
Absorption coefficient 19.482 mm"-1
F(000) 1616
Crystal size 0.36 x 0.32 x 0.24 mm
Theta range for data collection 2.06 to 30.00 deg.
Limiting indices -1<=h< 13, -1<=k<14, -28<I<28
Reflections collected 7334
Independent reflections 5713 [R(int) = 0.05321
Absorption correction Semi-empirical from psi-scans
Max. and mm. transmission 0.3420 and 0.2387
Refinement method Full-matrix least-squares on F'2
Data I restraints I parameters 5712/0/259
Goodness-of-fit on F"2 1.015
Final R indices [I>2sigma(1)] Ri = 0.0546, wR2 = 0.1092
R indices (all data) Ri =0.1073, wR2 = 0.1333
Largest duff, peak and hole 2.043 and -1.961 e.A"-3
Table 2. Atomic coordinates ( x 10"4) and equivalent isotropic displacement parameters (A"2 x 10'3) for 1. U(eq) is defined as one third of the trace of the orthogonalised Uij tensor
x y z U(eg) Os(1) 8185(1) 7231(1) 1834(1) 31(1)
8594(16) 5453(16) 1923(9) 54(4) 0(12) 8876(14) 4406(12) 1994(8) 82(4) C(11) 8324(15) 7727(15) 2767(7) 41(3) 0(11) 8454(13) 7972(15) 3322(6) 76(4)
10113(15) 7566(14) 1791(8) 42(3) 0(13) 11268(12) 7793(15) 1732(7) 76(4) Os(3) 5199(1) 7642(1) 1414(1) 31(1)
3917(15) 6199(16) 1362(8) 47(4) 0(31) 3139(14) 5349(13) 1309(7) 74(4) C(33) 4661(14) 8287(15) 2235(8) 46(4) 0(33) 4294(13) 8639(13) 2723(6) 66(3)
3860(19) 8747(16) 887(8) 56(4) 0(32) 3057(17) 9367(17) 582(9) 118(6) Os(2) 7296(1) 6881(1) 472(1) 37(1) C(21) 6439(21) 7392(18) -416(8) 62(5) 0(21) 5951(17) 7771(15) -928(6) 85(4) C(23) 6927(16) 5056(18) 418(9) 55(4) 0(23) 6714(15) 3986(13) 412(8) 82(4) C(22) 91 49(18) 6673(1 6) 240(8) 51(4) 0(22) 10274(14) 6573(16) 111(8) 92(5) F(1) 6194(12) 10529(10) 2157(5) 76(3)
7053(17) 10245(14) 1712(7) 44(3) C(2) 6852(14) 9035(14) 1402(7) 38(3) C(1) 7791(14) 8699(15) 902(6) 37(3) C(6) 8815(18) 9615(17) 756(8) 57(4)
8876(19) 10793(16) 1059(8) 57(4) 8008(20) 11116(15) 1546(9) 62(5)
Table 3. Bond lengths (A) and angles (deg) for 1.
Os(1)-C(13) 1.88(2) Os(1)-C(12) 1.90(2) Os(1)-C(11) 1.925(14) Os(1)-C(2) 2.358(13) Os(1)-C(1) 2.400(13) Os(1)-Os(2) 2.7554(8) Os(1)-Os(3) 2.8615(7) C(12)-0(12) 1.13(2) C(11)-0(11) 1.13(2) C(13)-0(13) 1.14(2) Os(3)-C(32) 1.91(2) Os(3)-C(33) 1.92(2) Os(3)-C(31) 1.93(2) Os(3)-C(2) 2.140(14) Os(3)-Os(2) 3.0417(8) C(31)-0(31) 1.15(2) C(33)-0(33) 1.14(2) C(32)-0(32) 1.11(2) Os(2)-C(22) 1.90(2) Os(2)-C(21) 1.92(2) Os(2)-C(23) 1.94(2) Os(2)-C(1) 2.11(2)
C(21)-0(21) 1.13(2) C(23)-0(23) 1.13(2) C(22)-0(22) 1.14(2)
F(1)-C(3) 1.33(2) C(3)-C(4) 1.36(2) C(3)-C(2) 1.41(2) C(2)-C(1) 1.48(2) C(1)-C(6) 1.42(2) C(6)-C(5) 1.37(2) C(5)-C(4) 1.41(2)
C(13)-Os(1)-C(12) 90.0(6) C(13)-Os(1)-C(1 1) 93.9(6) C(12).-Os(1)-C(1 1) 100.8(7) C(13)-Os(1)-C(2) 107.9(5) C(12)-Os(1)-C(2) 154.9(6) C(11)-Os(1)-C(2) 95.5(5) C(13)-Os(1)-C(1) 83.4(5) C(12)-.Os(1)-C(1) 134.7(6) C(11)-Os(1)-C(1) 124.3(6) C(2)-Os(1)-C(1) 36.2(5)
C(13)-Os(1)-Os(2) 97.8(5) C(12)-Os(1)-Os(2) 89.5(5) C(11)-Os(1)-Os(2) 164.4(4)
C(2)-Os(1)-Os(2) 71.0(3) C(1)-Os(1)-Os(2) 47.6(3)
C(13)-Os(1)-Os(3) 152.4(4) C(12)-Os(1)-Os(3) 110.7(5) C(11)-Os(1)-Os(3) 99.6(4) C(2)-Os(1)-Os(3) 47.2(3) C(1)-Os(1)-Os(3) 69.1(3) Os(2)-Os(1)-Os(3) 65.54(2) 0(12)-C(12)-Os(1) 178(2) O(11)-C(11)-Os(1) 176.6(14) 0(13)-C(13)-Os(1) 176.5(14) C(32)-Os(3)-C(33) 91.3(7) C(32)-Os(3)-C(31) 94.6(7) C(33)-Os(3)-C(31) 94.2(6) C(32)-Os(3)-C(2) 90.6(7) C(33)-Os(3)-C(2) 93.4(5) C(31)-Os(3)-C(2) 170.6(6) C(32)-Os(3)-Os(1) 143.0(6) C(33)-Os(3)-Os(1) 100.3(4) C(31)-Os(3)-Os(1) 119.2(5) C(2)-Os(3)-Os(1) 53.9(3)
C(32)-Os(3)-Os(2) 104.8(5) C(33)-Os(3)-Os(2) 155.0(4) C(31)-Os(3)-Os(2) 103.2(5) C(2)-Os(3)-Os(2) 67.9(4) Os(1)-Os(3)-Os(2) 55.55(2) 0(31)-C(31)-Os(3) 178(2) 0(33)-C(33)-Os(3) 177.2(13) 0(32)-C(32)-Os(3) 178(2) C(22)-Os(2)-C(21) 94.8(7) C(22)-Os(2)-C(23) 92.3(7) C(21)-Os(2)-C(23) 100.0(8) C(22)-Os(2)-C(1) 92.6(6) C(21)-Os(2)-C(1) 99.6(6) C(23)-Os(2)-C(1) 159.3(6) C(22)-Os(2)-Os(1) 95.8(5) C(21)-Os(2)-Os(1) 154.9(6) C(23)-Os(2)-Os(1) 102.2(5) C(1)-Os(2)-Os(1) 57.3(3) C(22)-Os(2)-Os(3) 153.8(5) C(21)-Os(2)-Os(3) 106.1(6) C(23)-Os(2)-Os(3) 99.3(5) C(1)-Os(2)-Os(3) 68.8(4) Os(1)-.Os(2)-Os(3) 58.91(2) 0(21)-C(21)Os(2) 176(2) 0(23)-C(23)-Os(2) 177(2) 0(22)-C(22)-Os(2) 178(2)
F(1)-C(3)-C(4) 121(2) F(1)-C(3)-C(2) 116.1(13)
C(4)-C(3)-C(2) 123(2) C(3)-C(2)-C(1) 117.1(13) C(3)-C(2)-Os(3) 131.0(11) C(1)-C(2)-Os(3) 111.2(10)
121.7(9) C(1)-C(2)-Os(1) 73.5(7) Os(3)-C(2)-Os(1) 78.9(5) C(6)-C(1)-C(2) 118.5(14) C(6)-C(1)-Os(2) 129.7(12) C(2)-C(1)-Os(2) 111.7(9) C(6)-C(1)-Os(1) 123.8(9) C(2)-C(1)-Os(1) 70.3(7) Os(2)-C(1)-Os(1) 75.1(5) C(5)-C(6)-C(1) 120(2) C(6)-C(5)-C(4) 122(2) C(3)-C(4)-C(5) 119(2)
Table 4. Anisotropic displacement parameters (A'2 x 10'3) for 1. The anisotropic displacement factor exponent takes the form: -2pi"2 [h"2 a*\2U11 +...+2hk a* b* U121
Ui! U22 U33 U23 U13 U12 Os(1) 26(1) 34(1) 33(1) 3(1) 2(1) 1(1)
42(8) 47(10) 76(11) 22(9) 19(8) 13(7) 0(12) 65(8) 45(8) 127(12) 14(8) -15(8) 17(6) C(11) 44(8) 44(8) 35(7) 3(6) 2(6) -3(7) 0(11) 66(8) 124(12) 39(6) -7(7) 13(6) 17(8)
32(7) 37(8) 53(9) -5(7) -5(6) 13(6) 0(13) 36(6) 119(12) 73(8) -9(8) 12(6) 8(7) Os(3) 26(1) 33(1) 34(1) 1(1) 2(1) 0(1)
42(8) 47(9) 55(9) 8(8) 18(7) -5(7) 0(31) 76(9) 63(8) 80(9) -3(7) 7(7) -27(7) C(33) 28(7) 47(9) 66(10) -9(8) 12(7) -11(6) 0(33) 68(8) 80(9) 57(7) -11(6) 35(6) 0(7)
63(10) 43(10) 58(10) 5(8) -.8(8) 17(8) 0(32) 95(11) 103(14) 138(14) 40(12) 41(10) 25(10) Os(2) 38(1) 39(1) 34(1) -5(1) 8(1) -6(1) C(21) 82(13) 69(12) 35(8) -9(8) 14(8) -21(10) 0(21) 105(12) 98(11) 45(7) 7(7) -11(7) 8(9) C(23) 41(9) 58(11) 65(11) -32(9) 3(8) -.6(8) 0(23) 82(9) 47(8) 119(12) -16(8) 21(8) -1(7) C(22) 55(9) 46(10) 54(9) 7(8) 15(8) -9(8) 0(22) 56(8) 114(13) 118(12) -28(10) 49(8) -1(8) F(1) 103(8) 58(7) 73(7) -18(5) 34(6) -10(6)
61(9) 34(8) 34(7) 6(6) 1(7) 1(7) C(2) 40(7) 38(8) 35(7) 5(6) 7(6) 8(6) C(1) 35(7) 51(9) 23(6) 6(6) -7(5) -6(6) C(6) 64(10) 56(11) 50(9) 12(8) 6(8) -26(9). C(S) 70(11) 39(9) 57(10) 13(8) -7(9) -12(8)
89(13) 31(8) 62(11) 1(8) -1(10) -28(9)
Table 5. Hydrogen coordinates (x 10"4) and isotropic displacement parameters (A"2 x 10'3) for 1.
x y z U(eg) H(6) 9442(18) 9414(17) 456(8) 68 11(5) 9511(19) 11400(16) 940(8) 69 H(4) 8088(20) 11918(15) 1751(9) 74 11(13) 6533(148) 7123(137) 2025(68) 50 11(23) 5477(147) 7041(135) 570(71) 50
Table 1. Crystal data and structure refinement for 0s 3(C0)9(ff)2(CJ13F)
Identification code siO21
Empirical formula C15 115 F 09 0s3
Formula weight 918.79
Temperature 293(2) K
Wavelength 0.71073 A
Crystal system Monoclinic
Space group P2(1)/c
Unit cell dimensions a = 9.4776(8) A alpha =90 deg.
b = 10.429(2) A beta 98.578(8) deg.
c = 20.023(2) A gamma =90 deg
Volume 1957.0(4) A
Z 4
Density (calculated) 3.118 Mg/m"3
Absorption coefficient 19.482 mm'-!
F(000) 1616
Crystal size 0.36 xO.32 x 0.24 mm
Theta range for data collection 2.06 to 30.00 deg.
Limiting indices -1<=h< 13, -1(k<14, -28<1<28
Reflections collected 7334
Independent reflections 5713 [R(int) = 0.05321
Absorption correction Semi-empirical from psi-scans
Max. and mm. transmission 0.3420 and 0.2387
Refinement method Full-matrix least-squares on F A 2
Data I restraints / parameters 5712/0/259
Goodness-of-fit on F A 2 1.015
Final R indices [I>2sigma([)] Ri = 0.0546, wR2 = 0.1092
R indices (all data) RI = 0.1073, wR2 = 0.1333
Largest diff. peak and hole 2.043 and -1.961 e.A"-3
Table 2. Atomic coordinates ( x 10'4) and equivalent isotropic displacement parameters (A'2 x 10A3) for 1. U(eq) is defined as one third of the trace of the orthogonalised Uij tensor
z U(eg) Os(1) 8185(1) 7231(1) 1834(1) 31(1)
8594(16) 5453(16) 1923(9) 54(4) 0(12) 8876(14) 4406(12) 1994(8) 82(4) C(11) 8324(15) 7727(15) 2767(7) 41(3) 0(11) 8454(13) 7972(15) 3322(6) 76(4)
10113(15) 7566(14) 1791(8) 42(3) 0(13) 11268(12) 7793(15) 1732(7) 76(4) Os(3) 5199(1) 7642(1) 1414(1) 31(1)
3917(15) 6199(16) 1362(8) 47(4) 0(31) 3139(14) 5349(13) 1309(7) 74(4) C(33) 4661(14) 8287(15) 2235(8) 46(4) 0(33) 4294(13) 8639(13) 2723(6) 66(3)
3860(19) 8747(16) 887(8) 56(4) 0(32) 3057(17) 9367(17) 582(9) 118(6) Os(2) 7296(1) 6881(1) 472(1) 37(1) C(21) 6439(21) 7392(18) 416(8) 62(5) 0(21) 5951(17) 7771(15) -928(6) 85(4) C(23) 6927(16) 5056(18) 418(9) 55(4) 0(23) 6714(15) 3986(13) 412(8) 82(4) C(22) 9149(18) 6673(16) 240(8) 51(4) 0(22) 10274(14) 6573(16) 111(8) 92(5) F(1) 6194(12) 10529(10) 2157(5) 76(3)
7053(17) 10245(14) 1712(7) 44(3) C(2) 6852(14) 9035(14) 1402(7) 38(3) C(1) 7791(14) 8699(15) 902(6) 37(3) C(6) 8815(18) 9615(17) 756(8) 57(4)
8876(19) 10793(16) 1059(8) 57(4) 8008(20) 11116(15) 1546(9) 62(5)
Table 3. Bond lengths (A) and angles (deg) for 1.
Os(1)-C(13) 1.88(2) Os(1)-C(12) 1.90(2) Os(1)-C(11) 1.925(14) Os(1)-C(2) 2.358(13) Os(1)-C(1) 2.400(13) Os(1)-Os(2) 2.7554(8) Os(1)-Os(3) 2.8615(7) C(12)-0(12) 1.13(2) C(11)-0(11) 1.13(2) C(13)-0(13) 1.14(2) Os(3)-C(32) 1.91(2) Os(3)-C(33) 1.92(2) Os(3)-C(31) 1.93(2) Os(3)-C(2) 2.140(14) Os(3)-Os(2) 3.0417(8) C(31)-0(31) 1.15(2) C(33)-0(33) 1.14(2) C(32)-0(32) 1.11(2) Os(2)-C(22) 1.90(2) Os(2)-C(21) 1.92(2) Os(2)-C(23) 1.94(2) Os(2)-C(1) 2.11(2)
C(21)-.0(21) 1.13(2) C(23)-0(23) 1.13(2) C(22)-0(22) 1.14(2)
F(1)-C(3) 1.33(2) C(3)-C(4) 1.36(2) C(3)-C(2) 1.41(2) C(2)-C(1) 1.48(2) C(1)-C(6) 1.42(2) C(6)-C(5) 1.37(2) C(5)-C(4) 1.41(2)
C(13)-Os(1)-C(12) 90.0(6) C(13)-Os(1)-C(1 1) 93.9(6) C(12)-Os(1)-C(1 1) 100.8(7) C(13)-Os(1)-C(2) 107.9(5) C(12)-Os(1)-C(2) 154.9(6) C(11)-Os(1)-C(2) 95.5(5) C(13)-Os(1)-C(1) 83.4(5) C(12)-Os(1)-C(1) 134.7(6) C(1 1)-Os(1)-C(1) 124.3(6) C(2)-Os(1)-C(1) 36.2(5)
C(13)-Os(1)-Os(2) 97.8(5) C(12)-Os(1)-Os(2) 89.5(5) C(1i)-Os(1)-Os(2) 164.4(4)
C(2)-Os(1)-Os(2) 71.0(3) C(1)-Os(1)-Os(2) 47.6(3) C(13)-Os(1)-Os(3) 152.4(4) C(12)-Os(1)-Os(3) 110.7(5) C(1 1)-Os(1)-Os(3) 99.6(4) C(2)-Os(1)-Os(3) 47.2(3) C(1)-Os(1)-Os(3) 69.1(3) Os(2)-Os(1)-Os(3) 65.54(2) 0(12)-C(12)-Os(1) 178(2) O(11)-C(11)-Os(1) 176.6(14) 0(13)-C(13)-Os(1) 176.5(14) C(32)-Os(3)-C(33) 91.3(7) C(32)-Os(3)-C(31) 94.6(7) C(33)-Os(3)-C(31) 94.2(6) C(32)-Os(3)-C(2) 90.6(7) C(33)-Os(3)-C(2) 93.4(5) C(31)-Os(3)-C(2) 170.6(6) C(32)-Os(3)-Os(1) 143.0(6) C(33)-Os(3)-Os(1) 100.3(4) C(31)-Os(3)-Os(1) 119.2(5) C(2)-Os(3)-Os(1) 53.9(3)
C(32)-Os(3)-Os(2) 104.8(5) C(33)-Os(3)-Os(2) 155.0(4) C(31)-Os(3)-Os(2) 103.2(5) C(2)-Os(3)-Os(2) 67.9(4) Os(1)-Os(3)-Os(2) 55.55(2) 0(31)-C(31)-Os(3) 178(2) 0(33)-C(33)-Os(3) 177.2(13) 032)-C32)-Os(3) 178(2) C(22)-Os(2)-C(21) 94.8(7) C(22)-Os(2)-C(23) 92.3(7) C(21)-Os(2)-C(23) 100.0(8) C(22)-Os(2)-C(1) 92.6(6) C(21)-Os(2)-C(1) 99.6(6) C(23)-Os(2)-C(1) 159.3(6) C(22)-Os(2)-Os(1) 95.8(5) C(21)-Os(2)-Os(1) 154.9(6) C(23)-Os(2)-Os(1) 102.2(5) C(1)-Os(2)-Os(1) 57.3(3)
C(22)-Os(2)-Os(3) 153.8(5) C(21)-Os(2)-Os(3) 106.1(6) C(23)-Os(2)-Os(3) 99.3(5) C(1)-Os(2)-Os(3) 68.8(4) Os(1)-Os(2)-Os(3) 58.91(2) 0(21)-C(21)-Os(2) 176(2) 0(23)-C(23)-Os(2) 177(2) 0(22)-C(22)-Os(2) 178(2)
F(1)-C(3)-C(4) 121(2) F(1)-C(3)-C(2) 116.1(13)
C(4)-C(3)-C(2) 123(2) C(3)-C(2)-C(1) 117.1(13) C(3)-C(2)-Os(3) 131.0(11) C(1)-C(2)-Os(3) 111.2(10) C(3)-C(2)-Os(1) 121.7(9) C(1)-C(2)-Os(1) 73.5(7) Os(3)-C(2)-Os(1) 78.9(5) C(6)-C(1)-C(2) 118.5(14) C(6)-C(1)-Os(2) 129.7(12) C(2)-C(1)-Os(2) 111.7(9) C(6)-C(1)-Os(1) 123.8(9) C(2)-C(1)-Os(1) 70.3(7) Os(2)-C(1)-Os(1) 75.1(5) C(5)-C(6)-C(1) 120(2) C(6)-C(5)-C(4) 122(2) C(3)-C(4)-C(5) 119(2)
Table 4. Anisotropic displacement parameters (A'2 x 10"3) for 1. The anisotropic displacement factor exponent takes the form: -2 piA2 [h"2 a*2 Ull +...+ 2 h k a* b* U121
Ull U22 U33 U23 U13 U12 Os(1) 26(1) 34(1) 33(1) 3(1) 2(1) 1(1)
42(8) 47(10) 76(11) 22(9) 19(8) 13(7) 0(12) 65(8) 45(8) 127(12) 14(8) -15(8) 17(6) C(11) 44(8) 44(8) 35(7) 3(6) 2(6) -3(7) 0(11) 66(8) 124(12) 39(6) -7(7) 13(6) 17(8)
32(7) 37(8) 53(9) -5(7) -5(6) 13(6) 0(13) 36(6) 119(12) 73(8) -9(8) 12(6) 8(7) Os(3) 26(1) 33(1) 34(1) 1(1) 2(1) 0(1)
42(8) 47(9) 55(9) 8(8) 18(7) -5(7) 0(31) 76(9) 63(8) 80(9) -3(7) 7(7) -27(7) C(33) 28(7) 47(9) 66(10) -9(8) 12(7) -11(6) 0(33) 68(8) 80(9) 57(7) -11(6) 35(6) 0(7)
63(10) 43(10) 58(10) 5(8) -8(8) 17(8) 0(32) 95(11) 103(14) 138(14) 40(12) 41(10) 25(10) Os(2) 38(1) 39(1) 34(1) -5(1) 8(1) -6(1) C(21) 82(13) 69(12) 35(8) -9(8) 14(8) -21(10) 0(21) 105(12) 98(11) 45(7) 7(7) -11(7) 8(9) C(23) 41(9) 58(11) 65(11) -32(9) 3(8) -6(8) 0(23) 82(9) 47(8) 119(12) -16(8) 21(8) -1(7) C(22) 55(9) 46(10) 54(9) 7(8) 15(8) -9(8) 0(22) 56(8) 114(13) 118(12) -28(10) 49(8) -1(8) F(1) 103(8) 58(7) 73(7) -18(5) 34(6) -10(6)
61(9) 34(8) 34(7) 6(6) 1(7) 1(7) C(2) 40(7) 38(8) 35(7) 5(6) 7(6) 8(6) C(1) 35(7) 51(9) 23(6) 6(6) -7(5) -6(6) C(6) 64(10) 56(11) 50(9) 12(8) 6(8) -26(9)
70(11) 39(9) 57(10) 13(8) -7(9) -12(8) 89(13) 31(8) 62(11) 1(8) -1(10) -28(9)
Table 5. Hydrogen coordinates (x 10''4) and isotropic displacement parameters (A¼2 x 10"3) for 1.
x y z U(eg) 11(6) 9442(18) 9414(17) 456(8) 68 11(5) 9511(19) 11400(16) 940(8) 69 11(4) 8088(20) 11918(15) 1751(9) 74
11(13) 6533(148) 7123(137) 2025(68) 50 11(23) 5477(147) 7041(135) 570(71) 50
Jk'-. .,
Table 1. Crystal data and structure refinement for clbos3 at 150(2) K.
Empirical formula C15 ff5 Cl 09 0s3
Formula weight 935.24
Wavelength 0.71073 A
Crystal system Triclinic
Space group P-i
Unit cell dimensions a = 8.666(5) A alpha = 100.04(3) deg. b = 9.309(5) A beta = 97.27(2) deg. c = 14.107(8) A ga = 116.83(3) deg.
Volume 972.3(9) A*3
Z 2
Density (calculated) 3.194 Mg/m^3
Absorption coefficient 19.736 mm-1
F(000) 824
Crystal description Yellow block
Crystal size 0.39 x 0.27 x 0.21 mm
Theta range for data collection 2.54 to 25.06 deg.
Index ranges -10<=h(=10, -11<k<10, 0<1<16
Reflections collected 3469
Independent reflections 3444 (R(int) = 0.0686]
Scan type
Absorption correction Difabs (Tmin= 0.827, Tmax=1.337)
Data / restraints / parameters 3441/0/255 (Full-matrix least-squares on F
Goodness-of-fit on F2 1.027
Conventional R [F>4sigma(F)] RI = 0.0365 [2876 data]
R indices (all data) Ri = 0.0502, wR2 = 0.0883
Extinction coefficient 0.0010(2)
Final maximum delta/sigma 0.001
Weighting scheme calc where P=(Fo2+2Fc2)/3
Largest diff. peak and hole 1.702 and -1.681 e.A-3
Table 2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (A2 x 103) for 1. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.
z y z U(eq)
1539(1) 998(1) 7989(1) 27(1) 3069(1) 22(1) 6596(1) 21(1)
08(3) 399(1) -2632(1) 7173(1) 26(1) Cl(l) 5965(5) 3511(4) 9684(3) 49(1)
5357(15) 1450(14) 9021(9) 28(3) 6509(16) 907(18) 9164(10) 40(3) 6062(17) -734(17) 8666(10) 37(3) 4447(17) -1742(15) 8015(9) 31(3) 3186(14) -1168(13) 7882(8) 23(2) 3612(15) 472(15) 8390(8) 25(2)
3053(20) 3219(17) 7994(11) 45(4) 0(11) 3953(19) 4579(13) 7958(9) 72(4)
1171(17) 1543(16) 9290(10) 36(3) 0(12) 1046(14) 1897(13) 10072(7) 52(3)
-453(22) 964(19) 7215(11) 45(4) 0(13) -1704(16) 873(17) 6720(9) 70(3)
5304(18) 1948(15) 6909(8) 30(3) 0(21) 6703(12) 3130(11) 7113(7) 46(3)
3731(17) -1317(17) 5718(10) 37(3) 0(22) 4081(15) -2162(13) 5208(8) 53(3)
2250(15) 929(16) 5692(9) 28(3) 0(23) 1811(13) 1565(12) 5184(7) 46(2)
614(18) -4438(16) 6414(11) 43(4) 0(31) 687(15) -5516(12) 5959(8) 56(3)
-29(16) -3741(14) 8234(9) 30(3) 0(32) -158(13) -4376(11) 8841(7) 43(2)
-2143(19) -3592(18) 6542(11) 46(4) 0(33) -3571(13) -4064(14) 6196(9) 63(3)
Table 3. Bond lengths [A] and angles [deg] for 1.
Os(1)-C(11) 1.882(14) Os(1)-C(13) 1.91(2) Os(1)-C(12) 1.924(13) Os(1)-C(6) 2.102(11) Os(l)-Os(2) 2.7502(13) Os(l)-Os(3) 3.010(2) 0s(2)-C(23) 1.880(13) Os(2)-C(21) 1.880(13) Os(2)-C(22) 1.92(2) Os(2)-C(5) 2.298(11) Os(2)-C(6) 2.439(11) Os(2)-Os(3) 2.852(2) Os(3)-C(31) 1.93(2) 09(3)-C(32) 1.943(13) Os(3)-C(33) 1.97(2) 08(3)-C(5) 2.152(11) C1(1)-C(1) 1.780(12) C(1)-C(2) 1.32(2) C(1)-C(6) 1.43(2) C(2)-C(3) 1.41(2) C(3)-C(4) 1.37(2) C(4)-C(5) 1.42(2) C(5)-C(6) 1.42(2) C(11)-0(11) 1.16(2) C(12)-0(12) 1.13(2) C(13)-0(13) 1.17(2) C(21)-0(21) 1.166(14) C(22)-0(22) 1.14(2) C(23)-0(23) 1.14(2) C(31)-0(31) 1.13(2) C(32)-0(32) 1.112(14) C(33)-0(33) 1.12(2)
C(11)-Os(1)-C(13) C(11)-Os(1)-C(12) C(13)-Os(1)-C(12) C(11)-Os(1)-C(6) C(13)-Os(1)--C(6) C(12)-Os(1)-C(6) C(11)-Os(1)-Os(2) C(13)-Os(1)-Os(2) C(12)-08(1)-Os(2) C(6)-Os(1)-Os(2) C (11)-Os (1)-Os (3) C(13)-Os(1)-Os(3) C(12)-Os(1)-Os(3) C(6)-Os(1)-Os(3) Os(2)-Os(1)-Os(3) C(23)-Os(2)-C(21) C(23)-Os(2)-C(22) C(21)-Os(2)-C(22) C(23)-Os(2)-C(5) C(21)-Os(2)-C(5) C(22)-Os(2)-C(5) C(23)-Os(2)-C(6) C(21)-Os(2)-C(6) C(22)-Os.(2)-C(6) C(5)-Os(2)-C(6) C(23)-0B(2)-Os(1) C(21)-0S(2)-OS(1)
92.1(7) 95.1(5) 99.7(6) 94.9(6)
160.5(5) 97.9(5) 88.0(4)
103.6(4) 156.4(4) 58.5(3)
147.2(4) 96.2(5)
114.5(4) 68.5(3) 59.16(3) 88.4(5) 99.7(5) 94.6(5)
159.6(4) 103.9(4) 95.5(5)
134.8(4) 82.9(4)
125.1(5) 34.8(4) 91.4(3) 99.9(4)
C(22)-Os(2)-Os(1) C(5)-Os(2)-Os(1) C(6)-Os(2)-Os(1) C(23)-Os(2)-Os(3) C(21)-Os(2)-Os(3) C(22)-Os(2)-Os(3) C(5)-Os(2)-Os(3) C(6)-Os(2)-Os(3) Os(1)-Os(2)-Os(3) C(31)-Os(3)-C(32) C(31)-Os(3)-C(33) C(32)-Os(3)-C(33) C(31)-Os(3)-C(5) C(32)-Os(3)-C(5) C (33)-Os (3)-C (5) C(31)-Os(3)-Os(2) C(32)-Os(3)-Os(2) C(33)-Os(3)-Os(2) C(5)-Os(3)-Os(2) C(31)-Os(3)-Os(1) C(32)-Os(3)-Os(1) C(33)-08(3)-Os(1) C(5)-Os(3)-Os(1) 09(2)-Os(3)-Os(1) C(2)-C(1)-C(6) C(2)-C(1)-C1(1) C(6)-C(1)-C1(1) C(1)-C(2)-C(3) C(4)-C(3)-C(2) C(3)-C(4)-C(5) C(6)-C(5)-C(4) C(6)-C(5)-Os(3) C(4)-C(5)-Os(3) C(6)-C(5)-Os(2) C (4)-C(S)-Os (2) Os(3)-C(5)-Os(2) C(5)-C(6)-C(1) C(S)-C(6)-Os(l) C(1)-C(6)-Os(1) C(5)-C(6)-Os(2) C (1)-C (6) -Os (2) Os(1)-C(6)-Os(2) O(11)-C(11)-Os(1) 0(12)-C(12)-Os(1) 0(13)-C(13)-Os(1) 0(21)-C (21)-Os (2) 0(22)-C(22)-Os(2) 0(23)-C(23)-Os(2) 0(31)-C (31)-Os (3) 0(32)-C(32)-Os(3) 0(33)-C(33)-Os(3)
162.0(4) 70.7(3) 47.3(3)
116.2(4) 150.2(3) 97.3(4) 47.9(3) 67.9(3) 64.96(4) 89.6(5) 93.8(6) 94.8(5) 94.8(5) 90.5(5)
169.9(6) 97.8(4)
142.6(3) 121.0(4) 52.4(3)
153.4(4) 109.1(3) 102.9(5) 67.2(3) 55.88(4)
124.2(12) 118.4(10) 117 .3(9) 120.1(12) 119.9(12) 119.8(11) 120.7(10) 111.0(8) 127 .4(8) 78.0(6)
118.5(8) 79.6(4)
115.1(10) 111.9(8) 132.9(9) 67.2(6)
122.3(8) 74.1(3)
177(2) 176.4(12) 177 .2(14) 178.8(11) 177.4(11) 176.0(11) 178.0(13) 174.8(12) 176.8(14)
Symmetry transformations used to generate equivalent atoms:
Table 4. Anisotropic displacement parameters (A'2 x 10'3) for 1. The anisotropic displacement factor exponent takes the form: -2 pi2 [ h2 a*2 Ull + ... + 2 h k a* b* U12 1
1.111 U22 U33 1123 U13 U12
30(1) 31(1) 29(1) 11(1) 13(1) 21(1) 21(1) 23(1) 22(1) 8(1) 7(1) 11(1) 23(1) 24(1) 26(1) 8(1) 7(1) 7(1)
C1(1) 45(2) 37(2) 43(2) -7(2) 2(2) 11(2) 21(6) 29(6) 27(6) 4(5) 6(5) 7(5) 21(6) 63(9) 40(8) 21(7) 8(6) 20(6) 33(7) 51(8) 40(8) 19(6) 9(6) 29(6) 46(8) 28(6) 38(7) 20(5) 21(6) 28(6) 18(5) 23(6) 31(6) 11(5) 4(5) 11(4) 27(6) 40(7) 24(6) 17(5) 12(5) 25(5)
65(10) 41(8) 58(9) 16(7) 42(8) 43(7) 0(11) 121(11) 33(6) 79(9) 21(6) 50(8) 43(7)
30(7) 40(7) 37(8) 11(6) 18(6) 14(6) 0(12) 57(7) 69(7) 39(6) 10(5) 19(5) 36(6)
65(10) 57(9) 39(8) 22(7) 35(8) 41(8) 0(13) 62(8) 109(10) 63(8) 20(7) 15(6) 63(8)
51(8) 29(6) 13(5) 6(4) 7(5) 23(6) 0(21) 40(5) 28(5) 45(6) 1(4) 12(4) -1(4)
37(7) 46(8) 30(7) 19(6) 13(6) 18(6) 0(22) 73(7) 53(6) 44(6) 10(5) 34(6) 35(6)
20(6) 44(7) 24(6) 2(5) 1(5) 23(5) 0(23) 43(6) 54(6) 48(6) 29(5) 9(5) 25(5)
31(7) 26(7) 48(8) 13(6) -1(6) -5(6) 0(31) 73(8) 32(5) 57(7) -2(5) 12(6) 25(5)
30(6) 28(6) 26(6) 0(5) -5(5) 14(5) 0(32) 51(6) 47(6) 33(5) 27(4) 14(4) 17(5)
28(8) 45(8) 51(9) 15(7) 9(6) 5(6) 0(33) 28(6) 67(7) 73(8) 31(6) 1(5) 3(5)
Table S. Hydrogen coordinates ( x 104) and isotropic displacement parameters (A'2 x 103) for 1.
x y z U(eq)
H(13) -48(1) -1153(1) 7995(1) 54(30) H(23) 767(1) -1728(1) 6101(1) 54(30) E(2) 7642(16) 1618(18) 9603(10) 48
6881(17) -1136(17) 8783(10) 45 4169(17) -2823(15) 7651(9) 37
Table 1. Crystal data and structure refinement for 3.
Identification code
Empirical formula
Formula weight
Temperature
Wavelength
Crystal system
Space group
Unit cell dimensions
Volume
os3tol
C16 H8 09 0s3
914.82
150 (2) K
0.71073 A
Triclinic
p-i
a = 9.260(2) A b = 13.115(2) A c = 16.633(3) A
2014.1(6) AA3
alpha.= 91.01(2) deg. beta .= 93.58(2) deg gamma = 92.23(2) deg
z
Density (calculated)
Absorption coefficient
F(000)
Crystal size
Theta range for data collection
Index ranges
Reflections collected
Independent reflections
Max. and mm. transmission
Refinement method
Data / restraints / parameters
Goodness-of-fit on F2
Final P. indices EI>2sigma(I)]
R indices (all data)
Largest diff. peak and hole
4
3.017 Mg/m""3
18.923 mm"'-1
1616
0.43 x 0.23 x 0.19 mm
2.59 to 27.53 deg.
-12<=h<=12, -17<=kcz=17, 0<=1<=21
9479
9234 [R(int) = 0.10361
0.037 and 0.007
Full-matrix least-squares on
9234 / 0 / 505
1.008
Ri = 0.0503, wR2 = 0.1215
Ri = 0.0786, wR2 = 0.1358
2.629 and -2.432 e.AA_3
Table 2. Atomic coordinates and equivalent isotropic displacement parameters (A2) for 1. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.
x y
VA
U(eq)
Os (1)
C(ll)
0(11) 0(12) 0(13) 0(21) 0(22) 0(23) 0(31) 0(32) 0(33) Os (4) Os(5) Os (6)
0(41) 0(42) 0(43) 0(51) 0(52) 0(53) 0(61)
0.00524(6) 0.30493(6) 0.23234(6)
-0.128(2) -0.126(2) -0.050(2) 0.369(2) 0.498(2) 0.297(2) 0.429(2) 0.191(2) 0.174(2) 0.262(2) 0.369(2) 0.370(2) 0.273(2) 0.181(2) 0.172(2) 0.474(2)
-0.2078(14) -0.1952(12) -0.0866(13) 0.407(2) 0.6141(13) 0.293(2) 0.5473 (14) 0.156(2) 0.1401(13) 0.18424(6) 0.48486(6) 0.25148(6) 0.116(2)
-0.008(2) 0.196(2) 0.610(2) 0.623(2) 0.545(2) 0.281(2) 0.313(2) 0.052(2) 0.229(2) 0.134(2) 0.137(2) 0.231(2) 0.323(2) 0.3.24 (2) 0.042(2) 0.0700 (14)
-0.1218(12) 0.2032 (14) 0.685(2) 0.7040 (14) 0.580(2) 0.303 (2)
0.28213 (4) 0.32711(4) 0.12338(4) 0.2521(10) 0.2354(11) 0.4196(12) 0.3037(13) 0.3295(11) 0.4718(13) 0.0904(12) 0.0741(11) 0.0029(11) 0.2294(11) 0.2271(12) 0.2995 (12) 0.3829(12) 0.3883 (12) 0.3076(10) 0.2953(13) 0.2416(9) 0.2034(9) 0.5021(8) 0.2910 (12) 0.3313(9) 0.5613 (8) 0.0697(10) 0.0497 (10)
-0.0704(9) 0.19575(4) 0.23378(4) 0.38207(4) 0.2510(11) 0.1759 (11) 0.0579(12) 0.3072 (12) 0.2429(11) 0.1040 (13) 0.4727(12) 0.4771(11) 0.4097 (13) 0.2493 (10) 0.2242(10) 0.1343 (13) 0.0572 (14) 0.0743(11) 0.1723(11) 0.109(2) 0.2862(9) 0.1626(9)
-0.0247(9) 0.3481(11) 0.2427(10) 0.0246(10) 0.5186(11)
0.39981(3) 0.43887(3) 0.40738(4) 0.3091(10) 0.4815 (10) 0.4068(9) 0.5474(11) 0.4101(9) 0.4411(10) 0.4162(11) 0.5131(10) 0.3473(8) 0.3134(9) 0.2523 (10) 0.1956(10) 0.2000 (10) 0.2600(9) 0.3202(9) 0.1302 (10) 0.2536(8) 0.5283(8) 0.4092 (7) 0.6125(8) 0.3897(7) 0.4454(8) 0.4204(9) 0.5747(8) 0.3105(7) 0.80842(3) 0.85053(3) 0.88328(4) 0.7114(10) 0.8402(8) 0.7668(10) 0.7789(10) 0.9411(11) 0.8189(11) 0.7938(11) 0.9685(11) 0.8869(13) 0.9513(8) 1.0097(10) 1.0498(9) 1.0245(10) 0.9632(9) 0.9252(9) 1.1170(12) 0.6517(8) 0.8614(8) 0.7457 (8) 0.7372(9) 0.9947(8) 0.7966(10) 0.7389(10)
0.03260 (13) 0.03348(13) 0.03382 (13) 0.040(3) 0.044(4) 0.041(3) 0.048(4) 0.039(3) 0.046(4) 0.045(4) 0.043(3) 0.038(3) 0.038(3) 0.044(4) 0.041(3) 0.049(4) 0.041(3) 0.035(3) 0.047(4) 0.056(3) 0.053(3) 0.051(3) 0.072(4) 0.052(3) 0.061(3) 0.063(3) 0.063(4) 0.051(3) 0.03324(13) 0.03461(13) 0.03594 (14) 0.042(3) 0.036(3) 0.045(4) 0.044(3) 0.042(4) 0.050(4) 0.051(4) 0.047(4) 0.056(5) 0.033(3) 0.039(3) 0.044(4) 0.050(4) 0.039(3) 0.037(3) 0.067(6) 0.056(3) 0.053(3) 0.056(3) 0.068(4) 0.062(3) 0.071(4) 0.081(5)
0(62) 0.3446(13) 0.5288(9) 1.0230(8) 0.052(3)
0(63) -0.067(2) 0.4260(11) 0.8886(12) 0.084(5)
Table 3. Selected bond lengths [A] and angles [deg] for 1.
Symmetry transformations used to generate equivalent atoms:
Table 4. Bond lengths [A] and angles [deg] for 1.
Os(l)-C(13) 1.90(2) Os(1)-C(11) 1.91(2) Os(l)-C(12) 1.97(2) Os(1)-C(76) 2.11(2) Os(l)-Os(2) 2.8470(10) Os(1) -Os (3) 3.0147(9) Os(2)-C(22) 1.88(2) Os(2)-C(21) 1.90(2) Os(2)-C(23) - 1.90(2) Os(2)-C(76) 2.27(2) Os(2)-C(71) 2.432(14) Os(2)-Os(3) 2.7627(9) Os(3)-C(31) 1.89(2) Os(3)-C(33) 1.90(2) Os(3)-C(32) 1.94(2) Os(3)-C(71) 2.13(2) C(11)-0(11) 1.15(2) C(12)-0(12) 1.12(2) C(13)-0(13) 1.15(2) C(21)-0(21) 1.14(2) C(22)-0(22) 1.14(2) C(23)-0(23) 1.18(2) C(31)-0(31) 1.13(2) C(32)-0(32) 1.14(2) C(33)-0(33) 1.15(2) C(71) -C(76) 1.36(2) C(71)-C(72) 1.46(2) C(72)-C(73) 1.35(2) C(73)-C(74) 1.45(2) C(73)-C(77) 1.50(2) C(74)-C(75) 1.36(2) C(75) -C(76) 1.47(2) Os(4)-C(41) 1.87(2) Os(4)-C(42) 1.90(2) Os(4)-C(43) 1.93(2) Os(4)-C(86) 2.30(2) Os(4)-C(81) 2.472(13) Os(4)-Os(6) 2.7544(9) Os(4)-Os(5) 2.8503(10) Os(5)-C(53) 1.89(2) Os(5)-C(52) 1.91(2) Os(5)-C(51) 1.95(2) Os(5)-C(86) 2.14(2) Os(5)-Os(6) 3.0308(10) Os(6)-C(63) 1.91(2) Os(6)-C(62) 1.92(2) Os(6)-C(61) 1.95(2) Os(6)-C(81) 2.104(13) C(41)-0(41) 1.17(2) C(42)-0(42) 1.14(2) C(43)-0(43) 1.14(2) C(51)-0(51) 1.14(2) C(52)-0(52) 1.13(2) C(53)-0(53) 1.16(2) C(61)-O(61) 1.13(2) C(62)-0(62) 1.14(2) C(63)-0(63) 1.13(2) C(81)-C{82) 1.38(2) C(81) -C(86) 1.45(2) C(82)-C(83) 1.37(2)
C(83) -C(84) -C(87) -C(85) -C(86)
C(13) -Os(1) -C(11) C(13) -Os(1) -C(12) C(11) -Os (1)-C(12) C(13) -Os(1) -C(76) C(11) -Os(1) -C(76) C(12) -Os (1)-C(76) C (13) -Os (1) -Os (2)
-Os(1) -Os(2) -Os (1) -Os (2)
C(76) -Os(1) -Os(2) -Os(1) -Os(3)
C(11) -Os(1) -Os (3) C(12) -Os(1) -Os(3) C(76) -Os (1) -Os (3) Os (2) -Os(1) -Os(3) C(22) -Os (2) -C(21) C(22) -Os(2) -C(23) C(21) -Os (2) -C(23) C(22) -Os(2) -C(76) C(21) -Os(2) -C(76) C(23)-Os(2) -C(76) C (22) -Os (2) -C (71) C(21) -Os(2) -C(71) C(23) -Os (2) -C(71) C(76) -Os (2) -C(71) C(22) -Os(2) -Os(3) C(21) -Os (2) -Os(3) C(23) -Os (2) -Os (3) C(76) -05(2) -Os(3) C(71)-Os(2) -Os(3)
-Os(2) -Os(1) C (21) -Os (2) -Os (1)
-Os (2) -Os (1) C(76) -05(2) -Os(1) C(71) -Os (2), -Os (1) Os (3) -Os (2) -Os (1) C(31) -Os (3)-C(33) C(31) -Os(3) -C(32)
-05(3) -C(32) -05(3) -C(71)
C(33) -Os(3) -C(71) -Os (3) -C(71)
C (31) -Os (3) -Os (2) -Os (3) -Os (2)
C(32)-Os(3) -Os(2) C(71) -Os(3) -Os(2)
-Os (3) -Os (1) C (33) -Os (3)-Os (1)
-Os(3) -Os(1) C(71) -Os (3) -Os(1) Os(2) -Os(3) -Os(1) O(11)-C(11) -Os(1) 0(12) -C(12) -Os ('1) 0(13) -C(].3) -Os (1) 0(21) -C(21) -Os (2) 0(22) -C (22) -Os (2) 0(23) -C(23) -Os (2) 0(31) -C(31) -Os(3) 0(32) -C(32) -Os(3)
1.44(2) 1.50(2) 1.38(2) 1.44(2)
92.7(6). 93.8(6) 95.7(7) 96.4(6) 89.3(6)
168.4(6) 95.1(5)
141.0(5) 121.7(5) 51.9(4)
151.2(5) 109.0(4) 102.4(4) 66.1(4) 56.15(2) 89.8(7) 93.3(7)
100.4(7) 104.6(6) 158.9(6) 94.3(5) 83.1(6)
138.0(6) 121.2(6) 33.3(4) 99.2(4) 93.2(5)
161.5(4) 69.5(3) 48.0(4)
150.2(4) 115.1(5) 97.6(5) 47.2(4) 67.5(4) 65.00(2) 93.7(7) 94.7(7) 97.7(6) 93.7(6)
101.3(5) 158.6(6) 91.1(5)
158.9(4) 102.3(4) 57.9(4)
149.6(5) 112.8(5) 96.1(4) 67.5(4) 58.85(2)
175.0(12) 175.5(14) 177.8(14) 179(2) 177.5(13) 178(2) 179 (2) 173.8(14)
0(33) -C(33) -Os(3) C(76) -C(71) -C(72) C(76) -C(71) -Os (3) C(72) -C(71) -Os (3) C(76) -C(71) -Os (2)
-C(71) -Os(2) Os (3) -C(71) -Os (2)
-C(72) -C(71) C(72) -C(73) -C(74) C(72)-C(73)-C(77) C(74)-C(73)-C(77) C(75)-C(74)-C(73) C(74)-C(75)-C(76) C(71) -C(76) -C(75) C(71)-C(76)-Os(1) C(75) -C(76) -Os(1) C(71) -C(76) -Os(2) C(75)-C(76) -Os(2) OS (1) -C(76) -Os (2) C(41) -Os (4) -C(42)
-Os (4) -C(43) C(42)-Os(4)-C(43) C(41)-Os(4)-C(86)
-Os(4) -C(86) -Os(4) -C(86) -Os (4)-C(81) -OS (4)-C(81)
C(43)-Os(4)-C(81) C(86) -Os (4) -C(81)
-OS (4) -Os (6) -Os(4) -Os(6) -Os(4) -Os(6)
C(86)-Os(4) -Os(6) C(81) -Os(4) -Os(6) C (41) -Os (4) -Os (5) C(42) -Os(4) -Os(5) C(43) -Os(4) -Os(5) C(86) -Os (4) -Os (5) C(81) -Os (4) -Os(5) Os(6) -Os(4) -Os(5) C(53)-Os(5)-C(52) C (53) -Os (5) -C(51) C (52) -Os (5) -C(51) C(53)-Os(5) -C(86) C(52) -Os(5) -C(86) C(51) -Os (5) -C(86) C(53) -Os(5) -Os(4)
-Os (5) -OS (4) C(51) -OS (5) -OS (4) C(86)-Os(5) -05(4)
-Os (5) -Os (6) C (52) -Os (5) -Os (6) C(51)-Os(5)-Os(6) C(86) -Os (5) -Os (6) OS (4) -Os(5) -Os(6) C(63) -Os(6) -C(62) C(63)-Os(6) -C(61)
-Os(6) -C(61) -Os (6) -C(81) -Os (6)-C(81)
C(61)-Os(6)-C(81) -Os(6) -Os(4)
C(62) -Os (6) -OS (4) C(61) -Os (6) -Os (4)
179 .2(14) 122 .2(14) 110.1(11) 127.6(10) 66.6(8)
122.2(11) 74.1(4)
119.8(14) 119 (2) 120.4(14) 120.3(14) 121 (2) 121 (2) 116.5(14) 114.8(11) 127.2(11) 80.0(9)
118.9(10) 81.0(5) 90.8(7) 95.8(7) 94.2(6)
160.7(6) 103.6(6) 95.9(7)
138.6(6) 82.1(5)
125.2(6) 35.1(5) 94.7(5) 98.9(4)
163.0(5) 70.6(3) 47.1(3)
115.3(5) 149.6(4) 97.9(5) 47.6(4) 68.2(3) 65.44(3) 92.7(7) 94.1(7) 94.5(7) 93.6(6) 90.2(6)
170.8(6) 96.4(5)
142.0(5) 121.3(5) 52.5(4)
151.8(5) 106.9(4) 104.2(5) 66.8(4) 55.75(2) 94.5(7) 93.9(8) 97.4(7) 92.4(7) 99.2(6)
161.8(6) 91.2(5)
158.1(5) 103.4(5)
C(81) -Os (6) -Os(4) 59.4(4) C(63) -Os (6) -OS (5) 149.5(5) C(62) -Os (6) -OS (5) 111.6(5) C(61) -Os (6) -05(5) 98.0(6) C (81) -Os (6) -Os (5) 68.8(4) Os(4) -Os (6) -Os (5) 58.80(2) 0(41) -C(41) -Os (4) 178 (2) O(42)-C(42)-Os(4) 177.9(14) 0(43)-C(43)-Os(4) 177(2) 0(51) -C(51) -Os (5) 178 (2) O(52)-C(52)-Os(5) 176.2(14) 0(53)-C(53)-Os(5) 178(2) O(61)-C(61)-Os(6) 174(2) O(62)-C(62)-Os(6) 174.8(13) O(63)-C(63)-Os(6) 180(2) C(82)-C(81)-C(86) 118.3(13) C(82)-C(81)-Os(6) 130.9(11) C(86)-C(81)-Os(6) 110.6(9) C(82)-C(81)-Os(4) 122.8(10) C(86)-C(81)-Os(4) 65.9(8) Os(6)-C(81) -OS (4) 73.5(4) C(83) -C(82) -C(81) 123.3(14) C(82)-C(83)-C(84) 119(2) C(82)-C(83)-C(87) 124(2) C(84)-C(83)-C(87) 117(2) C(85)-C(84)-C(83) 121(2) C(84)-C(85)-C(86) 119(2) C(85)-C(86)-C(81) 119.4 (13) C(85)-C(86)-Os(5) 127.0(11) C(81)-C(86)-Os(5) 112.1(9) C(85) -C(86) -Os(4) 120.4 (10) C(81)-C(86)-Os(4) 79.0(8) Os(5)-C(86) -Os(4) 79.8(5)
Symmetry transformations used to generate equivalent atoms:
Table 5. Anisotropic displacement parameters (A2) for 1. The anisotropic displacement factor exponent takes the form: -2 pi"2 E h"2 a*A2 Ui]. + . . . + 2 h k a* b* U12
Ui]. tJ22 U33. U23 U13 1J12
)s(1) 0.0315(3) 0.0333(3) 0.0332(3) 0.0013(2) 0.0024(2) 0.0029(2) )s(2) 0.0324(3) 0.0358(3) 0.0321(3) -0.0008(2) 0.0029(2) -0.0004(2) )s(3) 0.0346(3) 0.0325(3) 0.0347(3) 0.0027(2) 0.0029(2) 0.0030(2) :(l1) 0.045(8) 0.022(6) 0.053(10) -0.006(6) 0.003(7) 0.003(5)
0.048(9) 0.034(7) 0.049(10) -0.003(6) -0.004(7) 0.010(6) 0.045(9) 0.045(8) 0.033(8) 0.015(6) -0.008(6) 0.008(6) 0.045(9) 0.051(9) 0.047(10) -0.001(7) 0.017(7) -0.016(7) 0.043(9) 0.037(7) 0.036(8) -0.001(6) -0.008(6) 0.005(6) 0.037(8) 0.060(10) 0.039(9) 0.008(7) -0.017(7) 0.008(7)
:31) 0.038(8) 0.041(8) 0.056(10) 0.007(7) 0.006(7) 0.004(6) 0.046(9) 0.030(7) 0.052(10) 0.010(6) 0.008(7) 0.005(6) 0.061(10) 0.039(7) 0.018(6) 0.015(5) 0.010(6) 0.009(6) 0.040(8) 0.041(7) 0.031(7) -0.001(6) -0.013(6) 0.015(6) 0.038(8) 0.049(9) 0.046(9) -0.005(7) -0.001(7) 0.016(6)
'(73) 0.033(8) 0.044(8) 0.045(9) -0.001(7) -0.004(6) -0.003(6) 0.064(11) 0.048(9) 0.035(8) 0.011(7) 0.003(7) -0.010(8) 0.042(8) 0.045(8) 0.035(8) -0.001(6) 0.000(6) 0.001(6) 0.040(8) 0.031(6) 0.033(7) 0.001(5) 0.003(6) 0.000(5) 0.048(9) 0.051(9) 0.043(9) -0.001(7) 0.007(7) 0.001(7) 0.057(8) 0.048(6) 0.061(8) -0.005(6) -0.015(6) 0.009(5) 0.038(6) 0.067(8) 0.058(8) 0.013(6) 0.018(6) 0.001(5) 0.062(8) 0.038(6) 0.053(7) -0.005(5) 0.003(6) 0.005(5) 0.071(9) 0.110(12) 0.032(7) 0.006(7) -0.011(6) -0.013(8) 0.042(7) 0.071(8) 0.045(7) 0.013(6) 0.007(5) 0.007(5) 0.077(9) 0.035(6) 0.069(9) -0.005(6) 0.001(7) -0.011(6) 0.050(8) 0.073(9) 0.069(9) 0.007(7) 0.006(6) 0.018(6) 0.081(10) 0.061(8) 0.050(8) 0.022(6) 0.019(7) 0.019(7) 0.059(8) 0.049(6) 0.045(7) -0.004(5) -0.002(6) 0.001(5)
)s(4) 0.0352(3) 0.0334(3) 0.0310(3) 0.0009(2) 0.0018(2) -0.0011(2) )s(5) 0.0339(3) 0.0360(3) 0.0341(3) 0.0000(2) 0.0040(2) 0:0008(2) )s(6) 0.0383(3) 0.0311(3) 0.0382(3) 0.0005(2) 0.0010(2) 0.0015(2)
0.048(9) 0.035(7) 0.044(9) 0.005(6) 0.004(7) -0.005(6) 0.043(8) 0.037(7) 0.029(7) 0.002(5) 0.008(6) -0.005(6) 0.044(9) 0.050(9) 0.045(9) -0.005(7) 0.027(7) -0.004(7)
:(51) 0.039(8) 0.048(8) 0.044(9) 0.002(7) -0.003(7) 0.002(6) 0.036(8) 0.037(7) 0.054(10) -0.008(7) 0.016(7) 0.005(6) 0.050(10) 0.047(9) 0.053(10) 0.003(7) 0.015(8) -0.016(7) 0.056(11) 0.042(8) 0.053(11) 0.005(8) -0.021(8) -0.004(7) 0.041(8) 0.036(7) 0.067(11) -0.009(7) 0.042(8) -0.015(6) 0.058(12) 0.041(9) 0.069(13) 0.010(8) -0.006(9) 0.004(8) 0.039(7) 0.036(7) 0.023(6) -0.001(5) 0.005(5) -0.004(5) 0.037(8) 0.033(7) 0.047(9) -0.003(6) 0.007(6) -0.002(6) 0.045(9) 0.056(9) 0.030(8) 0.016(7) -0.002(6) -0.003(7) 0.049(10) 0.057(10) 0.042(9) 0.002(7) 0.003(7) -0.007(7)
:(85) 0.049(9) 0.034(7) 0.035(8) 0.007(6) -0.007(6) 0003(6) 0.045(8) 0.035(7) 0.031(7) 0.003(5) 0.004(6) 0.000(6) 0.066(13) 0.077(13) 0.059(12) 0.004(10) 0.026(10) -0.023(10) 0.062(8) 0.055(7) 0.051(7) 0.011(6) -0.002(6) -0.008(6) 0.040(6) 0.058(7) 0.061(8) -0.007(6) 0.012(6) -0.008(5) 0.070(8) 0.042(6) 0.056(8) -0.008(5) 0.001(6) -0.002(5) 0.061(8) 0.084(10) 0.059(9) 0.010(7) 0.010(7) -0.020(7) 0.051(7) 0.081(9) 0.053(8) -0.016(7) -0.016(6) 0.012(6) 0.067(9) 0.062(8) 0.085(11) -0.028(7) 0.005(8) 0.020(7)
)(61) 0.105(12) 0.059(8) 0.074(10) 0.020(8) -0.025(9) -0.021(8)
0.045(7) 0.049(6) 0.061(8) -0.015(6) 0.007(6) 0.001(5) 0.045(8) 0.067(9) 0.14(2) 0.015(9) 0.006(9) 0.023(7)
Table 6. Hydrogen coordinates and isotropic displacement parameters (AA2) for ]
x y
U(eq)
H(72)
H(77A) H(77B) H(77C) H(82)
H(87A) H(87B) H(87C)
0.436(2) 0.274(2) 0.123(2) 0.461(2) 0.457(2) 0.572(2) 0.065(2) 0.230(2) 0.383(2) 0.063(2) -0.058(2) 0.059(2)
0.1760(12) 0.4331(12) 0.4443 (12) 0.3522(13) 0.2328(13) 0.2982 (13) .0.2709(10) -0.0055(14) 0.0236 (11) 0.042(2) 0.109(2) 0.158(2)
0.2525 (10) 0.1612 (10) 0.2635(9) 0.0953 (10) 0.0996(10) 0.1538(10) 1.0219 (10) 1.0498 (10) 0.9468(9) 1.1362 (12) 1.0974(12) 1.1603 (12)
0.053 0.059 0.049 0.071 0.071 0.071 0.047 0.060 0.047 0.101 0.101 0.101
Table 1. Crystal data and structure refinement for nol98la at 150(2) K.
Empirical formula C17 510 09 0s3
Formula weight 928.85
Wavelength 0.71073 A
Crystal system Triclinic
Space group P-i
Unit cell dimensions a = 8.873(11) A alpha = 79.95(7) deg. b = 9.708(8) A beta = 73.56(8) deg. c = 13.644(12) A ga-ma = 64.88(8) deg.
Volume 1019(2) A3
2 2
Density (calculated) 3.028 Mg/m3
Absorption coefficient 18.710 mm-1
F(000) 824
Crystal description Yellow plate developed in (011)
Crystal size 0.23 x 0.16 x 0.06 mm
Theta range for data collection 2.61 to 22.48 deg.
Index ranges -8<h<9, -10<k<10, 0<=l<=14
Reflections collected 2341
Independent reflections 2333 [R(int) = 0.0822]
Scan type omega-theta
Absorption correction Psi-scans (Tmin= 0.277, Tmax=0.722)
Data / restraints / parameters 2330/0/179 (Full-matrix least-squares on F
Goodness-of-fit on F2 1.016
Conventional R (F>4sigma(F)J Ri = 0.0451 (1815 data]
R indices (all data) Ri = 0.0660, wR2 = 0.1143
Final maximum delta/sigma 0.002
Weighting scheme calc w=i/[\s'2(Fo'2')+(0.0709P)'2'+0.8654P] where P=(Fo2+2FC'2')/3
Largest diff. peak and hole 1.641 and -2.160 e.A-3
Table 2. Atomic coordinates ( x 10'4) and equivalent isotropic displacement parameters (A2 x 103) for 1. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.
x y z U(eq)
Os(l) -125(1) 4147(1) 2358(1) 16(1) 154(1) 1190(1) 2949(1) 18(1) 2363(1) 2448(1) 3561(1) 18(1) -1106(27) 4291(24) 1272(15) 21(5)
0(11) -1703(19) . 4379(17) 601(11) 30(4) 276(28) 6019(27) 1877(16) 25(5)
0(12) 496(20) 7090(18) 1613(11) 32(4) -2295(30) 5131(27) 3257(16) 23(5)
0(13) -3551(21) . 5678(19) 3846(12) 37(4) -1158(28) 1095(26) 2092(16) 24(5)
0(21) -1958(28) 1034(24) 1603(13) 62(7) 1409(31) -991(30) 3073(16) 29(5)
0(22) 2175(23) -2229(20) 3149(13) 48(5) -1718(33) 1410(30) 4158(18) 35(6)
0(23) -2926(22) 1671(23) 4811(12) 50(5) 3576(29) 3729(27) 3373(16) 28(5)
0(31) 4376(24) 4411(22) 3240(14) 52(5) 4375(30) 653(27) 3596(15) 23(5)
0(32) 5599(20) -408(19) 3615(12) 38(4) 1589(29) 2562(27) 5058(17) 28(5)
0(33) 1109(21) 2674(20) 5905(10) 37(4) 1791(25) 1763(23) 1666(14) 16(4) 2162(26) 1529(24) 599(14) 20(5) 3478(26) 1800(24) -101(14) 18(4)
C(30) 3800(28) 1495(26) -1233(15) 25(5) 4323(27) 2581(25) 148(15) 22(5)
c(40) 5796(31) 2843(29) -643(17) 36(6) 4014(26) 2831(24) 1154(15) 22(5) 2703(24) 2476(22) 1960(14) 14(4)
Table 3. Bond lengths [A] and angles [deg] for 1.
Os(1)-C(11) 1.88(2) Os(1)-C(13) 1.91(2) Os(1)-C(12) 1.97(2) Os(1)-C(6) 2.30(2) 08(1)-C(1) 2.38(2) Os(1)-Os(2) 2.766(3) Os(1)-Os(3) 2.881(4) Os(2)-C(21) 1.91(2) Os(2)-C(22) 1.93(3) Os(2)-C(23) 1.95(2) Os(2)-C(1) 2.10(2) Os(2)-Os(3) 3.056(3) Os(3)-C(32) 1.90(3) Os(3)-C(31) 1.91(2) Os(3)-C(33) 1.97(2) Os(3)-C(6) 2.12(2) C(l1)-0(11) 1.15(2) C(12)-0(12) 1.12(2) C(13)-0(13) 1.14(3) C(21)-0(21) 1.13(2) C(22)-0(22) 1.10(3) C(23)-0(23) 1.15(3) C(31)-0(31) 1.12(2) C(32)-0(32) 1.14(3) C(33)-0(33) 1.12(2) C(1)-C(6) 1.43(3) C(1)-C(2) 1.44(3) C(2)-C(3) 1.37(3) C(3)-C(4) 1.40(3) C(3)-C(30) 1.55(3) C(4)-C(5) 1.37(3) C(4)-.C(40) 1.53(3) C(5)-C(6) 1.47(3)
C(11)-Os(1)-C(13) C(11)-Os(1)-C(12) C(13)-Os(1)-C(12) C(11)-Os(1)-C(6) C(13)-Os(1)-C(6) C(12)-Os(1)-C(6) C(11)-Os(1)-C(1) C(13)-Os(1)-C(1) C(12)-Os(1)-C(1) C (6)-Os (1) -C (1) C(11)-Os(1)-0S(2) C(13)-Os(1)-0S(2) C(12)-Os(1)-Os(2) C(6)-0S(1)-0S(2) C(1)-Os(1)-OS(2) C (11)-Os (1)-Os (3) C(13)-Os(1)-Os(3) C(12)-Os(1)-Os(3) C(6)-Os(1)-Os(3). C(1)-Os(1)-Os(3) Os(2)-Os(1)-Os(3) C(21)-Os(2)-C(22) C(21)-Os(2)-C(23) C(22)-O8(2)-C(23) C(21)-Os(2)-C(1) C(22)-0S(2)C(1)
93.0(9) 93.2(8) 95.1(9)
108.4(8) 154.9(7) 96.5(8) 81.7(8)
142.8(8) 121.8(8) 35.6(6) 93.1(6) 96.7(6)
166.3(7) 69.9(4) 47.3(4)
150.4(7) 108.9(6) 104.0(6) 46.6(5) 68.9(5) 65.50(8) 94.5(10) 91.8(9) 99.0(10) 90.2(8)
100.2(9)
C(23)-Os(2)-C(1) C(21)-Os(2)-Os(1) C(22)-Os(2)-Os(1) C(23)-06(2)-Os(1) C(1)-Os(2)-Os(1) C(21)-Os(2)-Os(3) C(22)-Os(2)-Os(3) C(23)-Os(2)-Os(3) C( 1)-Os (2)-Os (3) Os(1)-Os(2)-Os(3) C (32 ) -Os (3)-C (31) C(32)-Os(3)-C(33) C(31)-Os(3)-C(33) C(32)-Os(3)-C(6) C (31)-Os (3)-C (6) C(33)-Os(3)-C(6) C(32)-Os(3)-Os(1) C(31) -Os (3 )-Os ( 1) C(33) -Os (3 )-Os ( 1) C(6)-Os(3)-Os(1) C(32)-Os(3)-Os(2) C(31)-Os(3)-08(2) C(33)-Os(3)-Os(2) C(6)-Os(3)-08(2) Os(1)-Os(3)-Os(2) 0(11)-C(11)-Os(1) 0(12)-C(12)-Os(1) 0(13)-C(13)-Os(1) 0(21) -C (21) -Os (2) 0(22)-C(22)-Os(2) 0(23)-C(23)-Os(2) 0(31)-C(31)-Os(3) 0(32)-C(32)-Os(3) 0(33)-C(33)-Os(3) C (6)-C (1)-C (2) C (6)-C (1)-Os (2) C (2) -C (1)-Os (2) C(6)-C(1)-Os(1) C(2)-C(1)-Os(1) Os(2)-C(1)-Os(1) C(3)-C(2)-C(l) C(2)-C(3)-C(4) C(2)-C(3)-C(30) C(4)-C(3)-C(30) C(S)-C(4)-C(3) C(5)-C(4)-C(40) C(3)-C(4)-C(40) C(4)-C(S)-C(6) C(1)-C(6)-C(5) C ( 1)-C (6)-Os (3) C(5)-C(6)-Os(3) C(1)-C(6)-Os(1) C(5)-C(6)-Os(1) Os(3)-C(6)-Os(1)
160.4(9) 97.3(6)
153 .8(6) 103.9(8) 56.6(6)
154.0(6) 103.4(6) 103 .6(7) 68.4(5) 59.06(7) 92.2(9) 95.0(9) 95.0(9) 93.6(8) 91.0(8)
169.3(8) 142.8(6) 101.4(7) 117.7(7) 52.2(5)
100.8(6) 154. 1(6) 105.9(6) 66.1(5) 55.44(7)
180(2) 179 (2) 176 (2) 179 (2) 177 (2) 173(2) 176 (2) 179(2) 178(2) 117 (2) 110.9(13) 131.8(14) 69.4(12)
122.0(14) 76.1(7)
122(2) 122(2) 118(2) 119(2) 118(2) 121(2) 120(2) 123(2) 118(2) 114.2(12) 126.9(13) 75.0(12)
122.9(13) 81.2(7)
Symmetry transformations used to generate equivalent atoms:
Table 4. Anisotropic displacement parameters (A'2 x 10'3) for 1. The anisotropic displacement factor exponent takes the form: -2 pi2 [ h2 a*2 Ull + ... + 2 h k a* b* U12 ]
Ull 1722 U33 U23 U13 U12
15(1) 19(1) 18(1) -2(1) -4(1) -9(1) 18(1) 20(1) 20(1) 0(1) -3(1) -12(1) 18(1) 21(1) 19(1) -2(1) -7(1) -10(1)
0(11) 33(10) 24(9) 35(9) 1(7) -15(7) -11(8) 0(12) 39(10) 30(10) 36(9) -2(8) 1(7) -28(9) 0(13) 33(10) 34(10) 43(9) -15(8) 4(8) -15(9) 0(21) 109(17) 97(17) 40(10) 11(11) -38(11) -91(16) 0(22) 51(13) 25(11) 59(11) 2(9) -11(9) -11(10) 0(23) 31(11) 75(15) 31(9) -6(9) 13(8) -22(11) 0(31) 60(13) 51(13) 69(12) -4(10) -21(10) -41(12) 0(32) 24(10) 31(11) 44(10) 1(8) -3(8) 0(9) 0(33) 51(12) 54(12) 17(8) -10(8) -11(7) -27(11)
Table S. Hydrogen coordinates ( x 104) and isotropic displacement parameters (A2 x 103) for 1.
x y z U(eq)
H(13) 507(1) 4282(1) 3511(1) 50 H(23) 1292(1) 1102(1) 3919(1) 50 E(2) 1478(26) 1178(24) 370(14) 23 H(30A) 4864(87) 594(88) -1416(32) 37 H(30B) 3896(166) 2380(63) -1674(16) 37 H(30C) 2843(81) 1316(145) -1326(25) 37 H(40A) 5341(34) 3633(128) -1161(68) 54 H(40B) 6580(107) 1892(54) -973(85) 54 H(40C) 6414(126) 3170(172) -304(26) 54 H(5) 4674(26) 3254(24) 1342(15) 26
Table 1. Crystal data and structure refinement for os3xyl at 150(2) K.
Empirical formula C17 H10 09 0s3
Formula weight 928.85
Wavelength 0.71073 A
Crystal system Triclinic
Space group P-i
Unit cell dimensions a = 8.257(3) A alpha = 90.70(3) deg. b = 9.114(4) A beta = 100.92(4) deg. c = 14.771(6) A gm = 109.80(3) deg.
Volume 1023.4(7) A3
Z 2
Density (calculated) 3.014 Ng/m3
Absorption coefficient 18.623 am-1
F(000) 824
Crystal description Yellow chip
Crystal size 0.25 x 0.16 x 0.16 mm
Theta range for data collection 2.67 to 30.07 deg.
Index ranges -11<=hc=11, -12<k<12, 0<=l<=20
Reflections collected 6781
Independent reflections 5984 [R(int) = 0.0815]
Scan type omega-theta
Absorption correction Psi-scans (Tmin= 0.034, Tnax=0.069)
Data / restraints I parameters 5980/0/265 (Full-matrix least-squares on F - :
Goodness-of-fit on F2 0.999
Conventional R (F)4sigaa(F)] RI = 0.0442 (4611 data]
R indices (all data) RI = 0.0660, wR2 = 0.1097
Extinction coefficient 0.0031(2)
Final maximum delta/sigma 0.006
Weighting scheme calc w1/(\s2(Fo2)+(0.0638P) 2+0.0000P] where P=(Fo2'+2Fc2)/3
Largest diff. peak and hole 2.963 and -2.067 e.A-3
Table 2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (A2 x 103) for 1. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.
X 7 z U(eq)
8064(1) 1739(1) 3333(1) 21(1) 6437(1) 3810(1) 2705(1) 21(1) 4303(1) 506(1) 3055(1) 21(1)
5855(13) 568(12) 2065(7) 25(2) 6709(12) 2115(11) 1803(6) 22(2) 7586(14) 2294(13) 1031(7) 27(2)
C(3M) 8448(17) 3867(14) 695(9) 39(3) 7532(15) 937(14) 572(7) 31(2) 6725(14) -583(13) 793(7) 28(2)
C(5M) 6765(16) -1960(13) 239(8) 34(2) 5917(14) -753(12) 1533(7) 30(2)
10183(15) 2802(13) 2953(8) 30(2) 0(11) 11503(11) 3465(11) 2722(7) 47(2)
8964(15) 2737(12) 4547(8) 29(2) 0(12) 9398(13) 3331(11) 5277(6) 44(2)
8536(13) -197(12) 3511(7) 26(2) 0(13) 8831(13) -1304(11) 3604(7) 46(2)
6436(14) 4849(13) 3872(8) 31(2) 0(21) 6519(13) 5438(11) 4573(6) 45(2)
8548(14) 5451(12) 2611(7) 27(2) 0(22) 9792(11) 6421(10) 2522(6) 40(2)
4903(15) 4614(12) 1890(7) 29(2) 0(23) 3981(12) 5025(11) 1362(6) 41(2)
2130(15) -41(14) 2134(8) 32(2) 0(31) 924(12) -348(12) 1574(6) 43(2)
3260(14) 856(13) 4077(8) 29(2) 0(32) 2705(13) 1134(11) 4674(6) 42(2)
4014(13) -1659(10) 3265(7) 22(2) 0(33) 3846(13) -2896(11) 3425(7) 48(2)
Table 3. Bond lengths [A] and angles (deg] for 1.
08(l)-C(11) 1.885(11) 09(l)-C(12) 1.895(11) Os(1)-C(13) 1.942(10) 05(l)-C(l) 2.306(10) Os(1)-C(2) 2.408(9) Os(l)-Os(2) 2.7425(12) Os(l)-Os(3) 2.8666(13) Os(2)-C(22) 1.904(10) 0s(2)-C(23) 1.913(11) Os(2)-C(21) 1.956(12) Os(2)-C(2) 2.123(10) Os(2)-Os(3) 3.0379(15) Os(3)-C(33) 1.941(9) Os(3)-C(31) 1.942(12) Os(3)-C(32) 1.948(11) Os(3)-C(1) 2.108(10) C(1)-C(2) 1.441(14) C(1)-C(6) 1.451(15) C(2)-C(3) 1.445(13) C(3)-C(4) 1.39(2) C(3)-C(3M) 1.51(2) C(4)-C(5) 1.39(2) C(5)-C(6) 1.368(15) C(5)-C(5M) 1.504(14) C(11)-0(11) 1.170(13) C(12)-0(12) 1.136(13) C(13)-0(13) 1.120(13) C(21)-0(21) 1.141(14) C(22)-0(22) 1.137(12) C(23)-0(23) 1.142(13) C(31)-0(31) 1.117(14) C(32)-0(32) 1.130(13) C(33)-0(33) 1.122(12)
C(11)-Os(1)-C(12) C(11)-Os(1)-C(13) C(12)-Os(1)-C(13) C(11)-Os(1)-C(1) C(12)-Os(1)-C(1) C(13)-Os(1)-C(1) C(11)-Os(1)-C(2) C(12)-Os(1)-C(2) C(13)-Os(1)-C(2) C(1)-Os(1)-C(2) C(11)-Os(1)-Os(2) C(12)-Os(1)-Os(2) C(13)-Os(1)-08(2) C(1)-Os(1)-Os(2) C (2) -Oi (1)-Os (2) C(1l)-Os(1)-Os(3) C(12)-Os(1)-Os(3) C(13)-Os(1)-Os(3) C(1)-Os(1)-Os(3) C(2)-Os( 1)-Os (3) Os(2)-Os(1)-09(3) C(22)-Os(2)-C(23) C(22)-Os(2)-C(21) C(23)-Os(2)-C(21) C(22)-Os(2)-C(2) C(23)-Os(2)-C(2)
92.2(5) 95.0(4)
100.3(4) 110.2(4) 154.0(4) 91.0(4) 84.1(4)
142.0(4) 117.7(4) 35.5(3) 95.4(3) 95.0(3)
161.2(3) 70.7(3) 48.2(2)
152.7(3) 108.1(4) 98.9(3) 46.6(3) 68.7(2) 65.54(3) 95.5(5) 89.7(4) 98.6(5) 96.6(4)
101.5(4)
C(21)-Os(2)-C(2) C(22)-Os(2)-Os(1) C(23)-09(2)-Os(1) C(21)-Oé(2)-Os(1) C(2)-Os(2)-Os(1) C(22)-08(2)-09(3) C(23)-Os(2)-Os(3) C(21)-Os(2)-Os(3) C (2) -Os (2) -Os (3) Os(1)-Os(2)-Os(3) C(33)-Os(3)-C(31) C(33)-08(3)-C(32) C(31)-Os(3)-C(32) C (33) -Os (3)-C (1) C(31)-Os(3)-C(1) C(32)-Os(3)-C(1)
-O (3)-Os ( 1) -Os (3)-Os ( 1) -Os (3)-Os ( 1)
C(1)-Os(3)-Os(1) C(33)-Os(3)-Os(2) C(31)-Os(3)-Os(2) C(32)-Os(3)-Os(2) C(1)-Os(3)-Os(2) Os(1)-Os(3)-Os(2) C (2)-C (1) -C (6) C (2)-C() -Os (3) C (6)-C (1)-Os (3) C(2)-C(1)-Os(1) C(6)-C(1)-08(1) Os(3)-C(].)-Os(1) C(1)-C(2)-C(3) C(1)-C(2)-Os(2) C(3)-C(2)-Os(2) C(1)-C(2)-09(1) C(3)-C(2)-Os(l) Os(2)-C(2)-Os(1) C(4)-C(3)-C(2) C(4)-C(3)-C(3M) C(2)-C(3)-C(3M) C(3)-C(4)-C(5) C(6)-C(S)-C(4) C(6)-C(5)-C(5M) C(4)-C(5)-C(5M) C(S)-C(6)-C(I) 0(11)-C(11)-08(1) 0(12)-C(12)-Os(l) 0(13)-C(13)-Os(1) 0(21)-C (21) -Os (2) 0(22)-C(22)-Os(2) 0(23)-C(23)-Os(2) 0(31) -C (31)-Os (3) 0(32)-C(32)-Os(3) 0(33)-C(33)-Os(3)
158.2(4) 95.1(3)
157.6(3) 101. 1(3) 57.7(2)
154.2(3) 107.8(3) 97.4(3) 68.4(3) 59.20(3) 93.6(5) 95.3(4) 94.8(5) 92.6(4) 93.7(4)
168.0(4) 98.5(3)
144.4(3) 117.1(3) 52.6(3)
152.9(3) 104.8(4) 102.6(3) 66.9(3) 55.26(3)
117.9(9) 114.0(7) 127 .3(7) 76.1(5)
119.5(7) 80.9(3)
119.4(9) 109.7(7) 130.9(7) 68.3(5)
122.6(7) 74.2(3)
117.1(10) 120.4(10) 122.4(10) 125.9(10) 117.1(10) 122.3(10) 120.6(10) 122.6(10) 179.7(10) 175.7(11) 178.7(10) 176.1(10) 177.6(10) 175.7(10) 176.8(10) 176.6(10) 177.0(10)
Symmetry transformations used to generate equivalent atoms:
Table 4. Anisotropic displacement parameters (A2 x 103) for 1. The anisotropic displacement factor exponent takes the form: -2 pi2 ( h2 a*2 Ull + ... + 2 h k a* b* U12 I
Ull U22 U33 U23 U13 U12
08(1) 17(1) 20(1) 24(1) 2(1) 3(1) 5(1) 19(1) 18(1) 26(1) 2(1) 5(1) 5(1) 17(1) 20(1) 24(1) 3(1) 5(1) 3(1)
20(4) 24(5) 25(5) -3(4) 2(4) 1(4) 21(4) 22(5) 22(4) 7(3) 3(3) 7(4) 24(5) 30(5) 25(5) 2(4) 7(4) 6(4)
C(3M) 44(7) 35(6) 39(6) 6(5) 18(5) 9(5) 36(6) 36(6) 27(5) 4(4) 11(4) 16(5)
C(S) 23(5) 27(5) 30(5) -10(4) 6(4) 4(4) C(5M) 36(6) 27(6) 36(6) -8(4) 11(5) 4(5) C(6) 28(5) 21(5) 30(5) -2(4) 4(4) -3(4)
33(6) 29(5) 34(5) 10(4) 8(4) 17(5) 0(11) 22(4) 50(6) 72(7) 14(5) 20(4) 12(4)
36(6) 20(5) 34(6) 2(4) 1(4) 15(4) 0(12) 49(5) 41(5) 31(4) -7(4) -5(4) 9(4)
23(5) 21(5) 37(5) 9(4) 10(4) 8(4) 0(13) 57(6) 34(5) 59(6) 13(4) 24(5) 26(4)
22(5) 30(6) 39(6) 0(5) 5(4) 4(4) 0(21) 47(5) 46(5) 43(5) -12(4) 16(4) 14(4)
25(5) 24(5) 30(5) 1(4) 9(4) 2(4) 0(22) 32(4) 29(4) 50(5) -2(4) 15(4) -4(3)
33(5) 20(5) 32(5) 7(4) 11(4) 4(4) 0(23) 44(5) 41(5) 37(4) 14(4) -1(4) 18(4)
33(6) 32(6) 31(5) -2(4) 8(5) 11(5) 0(31) 34(5) 57(6) 36(4) 1(4) 2(4) 15(4)
28(5) 28(5) 33(5) 8(4) 10(4) 11(4) 0(32) 55(6) 51(6) 32(4) 10(4) 22(4) 25(5)
23(4) 10(4) 28(5) 3(3) 1(4) 1(3) 0(33) 48(6) 29(5) 62(6) 10(4) 12(5) 9(4)
Table S. Hydrogen coordinates ( x 104) and isotropic displacement parameters (A2 x 103) for 1. H(l) and H(2) were placed by the program HYDEX.
x y z U(eq)
H(l) 6282(1) 811(1) 3942(1) 50 H(2) 4304(1) 2488(1) 2872(1) 50 H(3M1) 9596(53) 4397(47) 1102(38) 59 8(3)(2) 7702(58) 4504(41) 702(59) 59 H(3M3) 8607(110) 3725(16) 63(25) 59 H(4) 8097(15) 1054(14) 60(7) 37 H(5M1) 7967(27) -1771(47) 156(53) 51 H(5M2) 5978(91) -2103(66) -368(25) 51 H(5M3) 6375(114) -2904(23) 567(31) 51 H(6) 5374(14) -1778(12) 1705(7) 36
Table 1. Crystal data and structure refinement for os3fme at 220(2) K.
Empirical formula C18 Ell F 08 0s3
Formula weight 944.87
Wavelength 0.71073 A
Crystal system Monoclinic
Space group P2(1)/n
Unit cell dimensions a = 15.131(5) A alpha = 90 deg. b = 18.430(6) A beta = 101.36(4) deg. c = 15.297(5) A gamon = 90 deg.
Volume 4182(2) A3
Z 8
Density (calculated) 3.001 Mg/m3
Absorption coefficient 18.234 aa-1
F(000) 3360
Crystal description block Yellow
Crystal size 0.25 x 0.16 x 0.16 ma
Theta range for data collection 2.59 to 25.03 deg.
Index ranges -18c=hc=17, 0c=kc=21, 0c=lc=18
Reflections collected 9283
Independent reflections 7369 [R(int) = 0.0558]
Scan type omega-theta with learnt profile
Absorption correction Psi-scans + Difabs (Tain= 0.028, Taax=0.074)
Data / restraints / parameters 7314/0/553 (Full-matrix least-squares on F
Goodness-of-fit on F2 1.041
Conventional R (F)4sigma(F)] RI = 0.0643 [4240 data]
R indices (all data) RI = 0.1356, wR2 = 0.1442
Extinction coefficient 0.000025(8)
Final maximum delta/sigma 0.004
Weighting scheme caic w=l/(\s'2'(Fo'2')+(0.0327P)^2+71.3486P] where P=(F o 2*+2Fc 2)/3
Largest diff. peak and hole 2.053 and -2.111 e.A-3
Table 2 • Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (A'2 x 103) for 1. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.
x y z U(eq)
08(1) 6987(1) 9466(1) 6622(1) 45(1) Os(2) 7156(1) 10731(1) 7948(1) 49(1) 09(3) 8522(1) 10354(1) 7091(1) 46(1) C(1) 8046(16) 9897(14) 8351(14) 43(6) C(2) 8686(19) 9783(17) 9177(19) 61(8) F(2) 8705(12) 10324(12) 9813(11) 99(6) C(3) 9184(17) 9200(17) 9398(19) 63(8) C(4) 9210(20) 8653(17) 8804(23) 78(10) C(5) 8647(16) 8734(15) 7925(19) 57(8) C(6) 8097(16) 9349(15) 7712(20) •62(8) C(7) 5519(19) 9267(18) 6054(20) 71(9) C(8) 5857(25) 8709(25) 6603(25) 113(15) C(9) 6313(20) 8663(19) 7473(23) 74(10) C(10) 6686(24) 8121(23) 8008(31) 154(22) C(11) 6882(17) 10128(16) 5676(21) 61(8) 0(11) 6758(15) 10499(13) 5031(14) 99(9) C(21) 7488(16) 8778(14) 5986(18) 49(7) 0(21) 7865(14) 8312(12) 5651(15) 83(6) C(12) 7850(19) 11428(16) 8658(20) 65(9) 0(12) 8274(16) 11877(11) 9103(14) 82(7) C(22) 6367(20) 10549(13) 8727(18) 62(8) 0(22) 5914(14) 10408(12) 9240(13) 81(7) C(32) 6459(19) 11447(15) 7190(20) 58(8) 0(32) 6022(16) 11875(12) 6729(19) 105(9) C(13) 8271(20) 11211(18) 6358(20) 67(9) 0(13) 8146(17) 11688(12) 5913(14) 93(8) C(23) 9260(16) 9817(14) 6433(17) 49(7) 0(23) 9700(14) 9543(13) 5986(13) 85(7) C(33) 9496(26) 10797(17) 7759(17) 79(11) 0(33) 10073(14) 11094(13) 8246(14) 87(7) Os(4) 6483(1) 8302(1) 1728(1) 52(1) 08(5) 7850(1) 7065(1) 1822(1) 56(1) 09(6) 7018(1) 7395(1) 3210(1) 47(1)
8272(19) 7894(15) 2763(18) 55(7) 9127(26) 7966(20) 3356(20) 84(11)
F(2') 9788(20) 7499(19) 3391(24) 75(11) 9309(20) 8559(18) 3900(19) 66(8) 8684(20) 9086(18) 3962(19) 69(9) 7890(21) 9029(13) 3396(17) 49(7)
P(5') 7206(32) 9509(29) 3414(37) 160(21) 7612(20) 8412(16) 2785(16) 59(8) 5840(33) 8474(23) 242(28) 127(16) 6313(28) 9059(24) 612(24) 100(13) 7208(24) 9128(16) 1025(19) 65(8)
7682(24) 9755(21) 1426(24) 112(14) C(14) 5558(20) 7579(19) 1668(25) 86(11) 0(14) 4941(16) 7211(14) 1536(16) 100(8) C(24) 5822(15) 8928(13). 2271(19) 52(7) 0(24) 5447(12) 9362(10) 2649(13) 70(6) C(1S) 8578(20) 6362(17) 2479(23) 74(10) 0(15) 9040(17) 5911(14) 2878(20) 120(10) C(25) 8614(21) 7264(18) 1068(23) 85(11) 0(25) 9085(14) 7364(12) 524(14) 84(7) C(35) 7052(26) 6357(16) 1109(23) 77(11)
0(35) 6573(15) 5928(12) 778(16) 78(7) C(16) 6336(23) 6531(16) 3005(20) 70(10) 0(16) 5935(14) 5993(11) 2832(17) 86(7) C(26) 6387(19) 7891(18) 3937(16) 68(9)
0(26) 5903(14) 8156(12) 4399(13) 83(7)
C(36) 7781(19) 6968(14) 4160(21) 62(8)
0(36) 8310(13) 6724(12) 4751(14) 78(6)
Table 3. Bond lengths [A] and angles [deg] for 1.
Os(1)-C(21) 1.85(3) Os(1)-C(11) 1.88(3) 09(1)-C(6) 2.13(3) 08(1)-C(8) . 2.20(3) Os(1)-C(7) 2.25(3) 08(1)-C(9) 2.33(3) Os(1)-0s(3) . 2.816(2) Os(l)-Os(2) 3.067(2) 0s(2)-C(12) . 1.87(3) 09(2)-C(22) 1.88(3) 0s(2)-C(32) .1.93(3) Os(2)-C(i) 2.06(3) Os(2)-Os(3) 2.745(2) Os(3)-C(33) 1.81(3) 09(3)-C(23) 1.92(3) Os(3)-C(13) 1.93(3) 0s(3)-C(6) 2.23(3) Os(3)-C(1) 2.34(2) C(1)-C(6) 1.42(3) C(1)-C(2) 1.45(3) C(2)-C(3) 1.32(4) C(2)-F(2) 1.39(3) C(3)-C(4) 1.36(4) C(4)-C(5) 1.45(4) C(5)-C(6) 1.40(3) C(7)-C(8) 1.36(4) C(8)-C(9) 1.38(4) C(9)-C(10) 1.34(4) C(11)-0(11) 1.18(3) C(21)-0(21) 1.20(3) C(12)-0(12) 1.18(3) C(22)-0(22) . 1.17(3) C(32)-0(32) 1.17(3) C(13)-0(13) 1.11(3) C(23)-0(23)
0 1.16(3)
C(33)-0(33) 1.17(3) Os(4)-C(24) 1.83(3) 0s(4)-C(14) 1.92(3) Os(4)-C(6 1 ) 2.12(3) Os(4)-C(8') 2.18(3) Os(4)-C(9') 2.27(3) Os(4)-C(7 1 ) 2.31(4) Os(4)-Os(6) 2.805(2) Os(4)-Os(5) 3.062(2) 0s(5)-C(25) 1.82(3) Os(5)-C(15) 1.86(3) 0s(5)-C(35) 1.96(4) Oa(5)-C(1') 2.11(3) Os(5)-0s(6) 2.743(2) Os(6)-C(26) . 1.84(3) Os(6)-C(36) 1.84(3) 08(6)-C(16) 1.89(4) 08(6)-C(6') 0 2.23(3) 0.(6)-C(1') 2.33(2) C(1')-C(6') 1.39(4) C(1')-C(2 1 ) 1.43(4) C(2')-C(.3') 1.37(4) C(3')-C(4') 1.37(4) C(4')-C(5 1 ) 1.34(3) C(5')-C(6') 1.48(3)
C(7')-C(8') 1.35(5) C(8')-C(9') 1.38(4) C(9')-C(10') 1.43(4) C(14)-0(14) 1.14(3) C(24)-0(24) 1.20(3) C(15)-0(15) 1.18(3) C(25)-0(25) 1.21(3) C(35)-0(35) 1.12(4) C(16)-0(16) 1.17(3) C(26)-0(26) 1.22(3) C(36)-0(36) 1.17(3)
C(21)-Os(1)-C(11) C(21)-Os(1)-C(6) C(11)-08(1)-C(6) C(21)-Os( 1)-C(S) C(11)-05(1)-C(8) C (6) -Os (1)-C(S) C(21)-Os(1)-C(7) C(11)-Os(1)-C(7) C(6)-Os(1)-C(7) C(8)-Os(1)-C(7) C(21)-Os(1)-C(9) C(11)-08(1)-C(9) C(6)-02(1)-C(9) C(8)-08(1)-C(9) C(7)-Os(1)-C(9) C(21) -Os ( 1)-Os (3) C(11)-Os(1)-Os(3) C(6)-Os(1)-Os(3) C(8)-09(1)-Os(3) C(7)-Os(1)-Os(3) C (9)-Os (1)-OS (3)
-Os ( 1)-Os (2 ) C(11)-Os(1)-Os(2) C (6) -Os (1)-Os (2) C(S) -Os (1) -Os (2) C(7)-08(1)-08(2) C(9)-Os(1)-Os(2) Os(3)-Os(1)-Os(2) C(12)-Os(2)-C(22) C(12)-Os(2)-C(32) C(22)-Os(2)-C(32) C(12)-Os(2)-C(1) C(22)-08(2)-C(1) C(32)-Os(2)-C(1) C(12)-Os(2)-Os(3)
-Os (2)-Os (3) C(32) -Oi (2)-Os (3) C (1)-Os (2) -Os (3) C (12)-Os (2)-Os (1) C (22)-Os (2)-Os (1) C(32) -Os (2)-Os ( 1) C(1)-Os(2)-Os(1) Os(3)-Os(2)-Os(1) C(33)-O5(3)-C(23) C(33)-Os(3)-C(13) C(23)-Os(3)-C(13) C(33)-Os(3)-C(6) C (23)-Os (3)-C (6) C (13)-Os (3)-C (6) C (33)-Os (3)-C (1) C (23)-Os (3)-C (1) C(13)-Os(3)-C(1)
91.2 (11) 90.0(11)
127.1(11) 87.5(14)
117.0(13) 115 .9 (13) 99.3(11) 83.2(11)
148.3(11) 35.6(12) 97.3(11)
149.6(12) 82.1(11) 35.2(11) 66.8(11) 97.5(8) 76.1(8) 51.4(7)
166.1(10) 153 .5 (9) 130.9(9) 151.6(8) 89.9(9) 67.0(7)
117.0(11) 109.1(7) 95.9(9) 55 .43 (4) 96.2(11) 93.3(12) 99.4(12) 94.5(12) 97.5(11)
160.1(10) 93.5(9)
153 .0 (9) 105 .1(8) 56.2(6)
150 .7 (9) 107.7(7) 99.1(8) 66.1(7) 57.63(4) 92.0(12) 90.2(14)
100.7(11) 113.8(12) 92.4(10)
152.3(11) 92.6(11)
123.5(10) 135.6(10)
C(6)-0s(3)-C(1) C(33)-Os(3)-Os(2) C(23)-Os(3)-Os(2) C(13)-Os(3)-Os(2) C(6) -Os (3)-OS (2) C(1)-Os(3)-Os(2) C(33)-Os(3)-Os(1) C(23)-09(3)-'Os(l) C(13)-Os(3)-Os(1) C(6)-Os(3)-Os(1) C(1)-Os(3)-Os(1) Os(2)-Os(3)-Os(1) C(6)-C(1)-C(2) C (6)-C (1) -Os (2) c (2)-c (1) -Os (2) C(6)-C(1)-Os(3) C(2)-C(1)-'0s(3) Os(2)-C(1)-Os(3) C(3)-C(2)-F(2) C(3)-C(2)-C(l) F(2)-C(2)-C(l) C(2)-C(3)-C(4) C(3)-C(4)-C(S) C(6)-C(5)-C(4) C(5)-C(6)-C(l) C(5)-C(6)-Os(l) C(1)-C(6)-Os(1) C(5)-C(6)-Os(3) C(1)-C(6)-Os(3) Os(1)-C(6)-Os(3) C(8)-C(7)-Os(1) C(7)-C(8)-C(9) C(7)-C(8)-Os(1) C(9)-C(8)-Os(1) C(10)-C(9)-C(8) C(10)-'C(9)-Os(1) C(8)-C(9)-08(1) 0(11)-C(11)-Os(1) 0(21)-C(21)-Os(1) 0(12)-C(12)-Os(2) 0(22)-C(22)-09(2) 0(32)-C(32)-Os(2) 0(13)-C(13)-Os(3) 0(23)-C(23)-Os(3) 0(33)-C(33)-Os(3) C(24)-Os(4)-C(14) C(24)-Os(4)-C(6 1 )
C(14)-Os(4)-C(6 1 )
C(24)-Os(4)-C(8 1 )
C(14)-Os(4)-C(8') C(6' )-Os(4)-C(8') C(24)-Os(4)-C(9 1 )
C(14)-Os(4)-C(9 1 )
C(6')-Os(4)-C(9 1 )
C(8' )-Os(4)-C(9') C(24)-0S(4)-C(7') C(14)-0s(4)-C(7 1 )
C(6')-Os(4)-C(7 1 )
C(8')-Os(4)-C(7 1 )
C(9')-09(4)-C(7 1 )
C(24)-Os(4)-Os(6) C(14)-0i(4)-Os(6) C(6')-Os(4)-Os(6) C(8')-09(4)-Os(6)
36.0(8) 102.8(10) 162. 1(7) 89.4(8) 72.6(6) 46.9(6)
160.6(g) 95.9(7)
105.6(9) 48.3(7) 68.3(6) 66.93(4)
112(2) 116.5(19) 131(2) 67.8(14)
120.6(16) 76.9(7)
118(3) 126(3) 115(3) 122(3) 117(3) 121(3) 122(3) 127(2) 109.0(19) 124.0(17) 76.2(14) 80.3(11) 70(2)
134(4) 74(2) 77.6(19)
135(4) 129(2) 67.2(18)
174(2) 174(2) 179(3) 176(3) 179(3) 177(3) 174(2) 174(3) 90.1(13) 91.3(11)
125.0(12) 87.7(14)
115.7(16) 119.3(14) 98.6(10)
149.2(14) 84.5(12) 36.2(11)
101.4(14) 83.5(16)
149.0(14) 34.9(12) 65.8(13) 96.1(8) 73.6(10) 51.6(7)
170.1(11)
C(9' )-Os(4)-Os(6)
C(7' )-Os(4)-Os(6)
C(24)-09(4)-Os(5)
C(14)-Os(4)-Os(5)
C(6' ) -On (4) -On (5) C(8' )-Os(4)-Os(5) C(9' )-Os(4)-Os(5) C(7' )-Os(4)-Os(5) Os(6)-Os(4)-Os(5) C(25)-Os(5)-C(15) C(25)-O&(5)-C(35) C(15)-OS(5)-C(35) C(25)-Os(5)-C(1 1 )
C(15)-08(5)-C(1 1 )
C(35)-Os(5)-C(1 1 )
C(25)-Os(5)-Os(6) C(15)-0.(5)-Os(6) C(35)-Os(5)-O.(6) C(1' )-Os(5)-Os(6) C(25)-Os(5)-Os(4) C(15)-Os(5)-Os(4) C(35)-Os(5)-0s(4) C(1' )-Os(5)-Os(4) 09(6)-Os(5)-Os(4) C(26)-Os(6)-C(36) C(26)-Os(6)-C(16) C(36)-0B(6)-C(16) C(26)-0s(6)-C(6 1 )
C(36)-Os(6)-C(6 1 )
C(16)-08(6)-C(6 1 )
C(26)-O.(6)-C(1') C(36)-Os(6)-C(1 1 )
C(16)-Os(6)-C(1 1 )
C(6')-Os(6)-C(1') C(26) -05 (6 )-Os (5) C (36)-Os (6)-Os (5) C(16)-08(6)-Os(5) C(6' )-Os(6)-Os(5) C(1' )-Os(6)-Os(5) C(26)-Os(6)-Os(4) C(36) -Os (6 )-Os (4) C(16)-Os(6)-Os(4) C(6' )-Os(6)-Os(4) C(1' )-Os(6)-Os(4)
Os(5)-Os(6)-Os(4)
C(6' )-C(1' )-C(2')
C(6' )-C(1' )-Os(5) C(2' )-C(1' )-Os(5) C (6' ) -C(1' ) -Oi (6) C (2' ) -C (1' ) -Oi (6) Os(5)-C(1' )-Os(6) C(3' )-C(2' )-C(1')
C(2' )-C(3' )-C(4')
C(5' )-C(4')-C(3') C(4' )-C(5' )-C(6')
C(1' )-C(6' )-C(5')
C(1' )-C(6' )-Os(4) C(5' )-C(6' )-Os(4) C(1' )-C(6' )-Os(6) C(5' )-C(6' )-Os(6) Os(4)-C(6' )-Os(6) C(8' )-C(7 ' )-Os(4) C(7')-C(8')-C(9') C(7' )-C(8' )-Os(4)
133.9(9)
151.1(11)
150.8(8)
88.0(9)
66.4(8) 119.1(11)
97.8(8) 107.3(11) 55.54(4) 95.8(13)
100.4(14) 94.1(14) 98.2(13) 93.9(13)
158.9(12) 153.0(10) 92.8(9)
104.6(9) 55.6(7)
109.2(10) 149.9(9) 97.6(9) 66.7(8) 57.46(4) 93.2(12)
100.8(12) 90.5(13) 92.6(12)
111.2(11) 153.9(11) 122.0(12) 88.8(11)
137.2(10) 35.3(9)
161.4(9) 101.7(9) 90.2(8) 71.8(7)
48.3(7)
95.2(8) 158.0(8)
107.9(9)
48.1(7)
69.5(7)
67.00(4)
119(3)
113(2)
128(2)
68.4(15)
122.5(19)
76.1(9)
121(4)
123(3)
116(3)
125(3)
115(3)
113(2)
130(2)
76.2(16)
122.9(17)
80.2(10)
67(2)
131(4)
78(3)
)-C(8' )-Os(4)
75.3(18) C(8')-C(9')-C(10')
129(4) C(8' )-C(9' )-Os(4)
68.5(18) )-C(9')-Os(4)
126(2) 0(14)-C(14)-Os(4)
170(3) 0(24)-C(24)-OB(4)
175(2) 0(15)-C(15)-Os(5)
179(3) 0(25)-C(25)-Os(5)
175(3) 0(35)-C(35)-O.(5)
173(3) 0(16)-C(16)-OS(6)
176(3) 0(26)-C(26)-Os(6)
173(3) 0(36)-C(36)-Oa(6)
176(2)
Byunetry transformations used to generate equivalent atoms:
Table 4. Anisotropic displacement parameters (A2 x 10'3) for 1. The anisotropic displacement factor exponent takes the form: -2 pi*2 [ h2 a*2 Ull + ... + 2 h k a* b* U12 ]
Ull U22 U33 U23 U13 U12
05(1) 38(1) 49(1) 46(1) -5(1) 6(1) -5(1) Os(2) 51(1) 45(1) 50(1) -6(1) 12(1) -3(1) Os(3) 41(1) 52(1) 42(1) 0(1) 5(1) -7(1)
50(15) 61(17) 18(11) 13(12) 6(11) -19(13) 54(18) 68(21) 63(20) -21(17) 19(16) -8(16)
F(2) 82(13) 135(18) 66(12) 5(13) -21(10) -4(13) 44(17) 85(23) 66(20) -14(18) 26(15) 14(16) 62(21) 68(22) 116(29) 39(21) 44(21) 29(17)
C(S) 36(15) 70(20) 66(19) 23(16) 9(14) 31(14) C(6) 27(14) 64(19) 94(22) -45(17) 10(14) -21(14) C(7) 66(21) 96(25) 60(20) -18(19) 32(17) -14(19) C(8) 90(29) 163(42) 77(27) 33(28) -6(22) -73(28) C(9) 51(19) 93(26) 82(24) 13(21) 22(18) -29(18) C(10) 68(26) 175(46) 225(54) 132(43) 43(31) 7(28) C(11) 32(15) 69(21) 81(22) -7(17) 8(15) -21(14) 0(11) 94(17) 112(20) 74(16) 38(14) -27(13) -65(15) C(21) 40(15) 39(15) 71(19) 14(14) 23(14) -2(12) 0(21) 74(15) 72(15) 104(18) -18(14) 24(13) -12(12) C(12) 62(20) 64(20) 68(21) 10(17) 11(16) -36(17) 0(12) 109(18) 64(15) 75(15) -12(12) 20(13) -31(13) C(22) 90(23) 36(15) 53(18) -31(14) -3(16) -30(15) 0(22) 88(15) 103(18) 57(13) 3(12) 31(12) -22(14) C(32) 48(18) 43(17) 81(22) 1(16) 8(16) -18(14) 0(32) 77(17) 63(16) 170(27) 12(16) 10(17) 18(13) C(13) 63(20) 87(24) 59(20) 6(18) 29(17) -19(18) 0(13) 143(22) 69(16) 64(15) 21(12) 11(14) -15(15) C(23) 32(15) 55(17) 53(17) 11(14) -7(12) -17(13) 0(23) 69(14) 124(20) 62(14) -17(14) 12(11) 0(14) C(33) 138(32) 74(22) 20(14) -22(15) 3(17) -34(22) 0(33) 77(16) 128(21) 58(14) -13(14) 20(12) -26(15) Os(4) 61(1) 49(1) 46(1) 4(1) 9(1) 9(1) Os(5) 64(1) 48(1) 61(1) 3(1) 26(1) 7(1) 09(6) 45(1) 49(1) 48(1) 5(1) 13(1) 4(1)
62(19) 50(17) 57(18) 11(15) 20(16) -9(15) 101(29) 94(27) 55(20) -15(20) 7(20) -68(24)
F(2'). 38(18) 81(26) 109(29) -16(22) 20(19) 2(18) 52(19) 85(23) 61(20) 4(18) 13(15) 1(18) 57(19) 95(25) 47(18) 7(17) -7(15) -5(19) 75(21) 25(13) 41(15) 2(12) -2(14) -13(14)
P(5') 106(37) 144(46) 195(53) 5(41) -56(36) -23(35) 77(21) 58(19) 40(16) 0(14) 3(15) 2(16) 164(46) 104(35) 121(38) 7(29) 52(34) -5(33) 100(33) 118(36) 75(27) 60(25) -1(23) 11(27) 93(26) 54(19) 53(19) 5(15) 25(18) -7(18)
C(10 1 ) 102(30) 135(37) 110(31) -9(28) 45(25) -37(28) C(14) 43(18) 78(24) 122(31) 29(22) -19(19) 0(18) 0(14) 77(16) 122(22) 92(18) 11(16) -5(14) -23(16) C(24) 25(14) 35(15) 96(22) 24(15) 15(14) 9(12) 0(24) 57(12) 55(12) 92(16) 13(11) -1(11) 29(11) C(15) 55(20) 66(21) 115(28) 27(20) 50(20) 23(17) 0(15) 90(20) 100(21) 179(29) 18(19) 47(19) 41(16) C(25) 86(24) 79(24) 106(28) -17(20) 56(22) 30(19) 0(25) 78(15) 104(18) 76(15) 10(13) 26(13) -2(14) C(35) 120(32) 38(18) 82(25) 15(17) 46(24) 29(19)
0(35) 82(17) 59(15) 99(18) 1(13) 28(14) -20(12) C(16) 105(27) 47(18) 69(21) -9(16) 42(19) 41(19) 0(16) 73(15) 55(14) 129(21) 15(14) 19(14) -16(12) C(26) 75(21) 105(25) 27(15) 16(16) 17(14) 4(19) 0(26) 92(16) 107(18) 54(13) -9(12) 24(12) 25(14) C(36) 55(18) 52(18) 80(22) 40(16) 16(16) 14(15) 0(36) 67(14) 95(16) 75(15) 43(13) 22(12) 25(13)
Table 5. Hydrogen coordinates ( x 10*4) and isotropic displacement parameters (A*2 x 10*3) for 1.
x y X. U(eq)
H(18) 6403(1) 10106(1) 7225(1) 43(60) 9529(17) 9160(17) 9979(19) 75 9575(20) 8241(17) 8957(23) 94 8651(16) 8372(15) 7493(19) 69
H(7A) 5087(19) 9587(18) 6263(20) 86 E(78) 5360(19) 9158(18) 5416(20) 86
5755(25) 8253(25) 6325(25) 136 5973(20) 8964(19) 7830(23) 89
H(1OA) 6950(24) 8315(23) 8590(31) 231 H(1OB) 7153(24) 7890(23) 7752(31) 231 B(IOC) 6227(24) 7768(23) 8067(31) 231 H(2B) 7097(1) 7698(1) - 1111(1) 165(142)
9567(26) 7604(20) 3371(20) 101 9891(20) 8607(18) 4248(19) 79 8806(20) 9466(18) 4378(19) 83 7477(21) 9411(13) 3386(17) 58
H(7'1) 6096(33) 8197(23) -196(28) 152 H(7'2) 5182(33) 8523(23) 92(28) 152
5976(28) 9490(24) 583(24) 120 7588(24) 8869(16) 668(19) 78
H(1OD) 8306(24) 9629(21) 1661(24) 169 H(10E) 7405(24) 9928(21) 1908(24) 169 H(10F) 7657(24) 10134(21) 982(24) 169
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