I

CHAPTER I

GENERAL INTRODUCTION

During the last few decades or so coordination chemistry has taken a

new turn and activities at its interface with material science have accelerated

exponentially. The continuing drive to scale down dimensions of electronic

devices has been a motivating factor for such a turn. A large number of

papers describing the preparation and characterization of metal complexes

have appeared in journals during this period. One of the important reasons for

this has been wide and varied applications of these compounds in different

fields. The emergence of excellent theories of electronic structure and the

advent of improved and newer techniques and the availability of sophisticated

physico-chemical instruments have also contributed to the development of

coordination chemistry1-4. These theories have helped in providing insight into

the spectral, magnetic and other properties of coordination complexes. New

coordination compounds, new theories and new applications have all helped

for the development of this area of chemistry.

The ligand field and molecular orbital theories have been successfully

applied to coordination complexes5•10. The spectral and magnetic properties

of the metal complexes can be corroborated by the application of these

theories. The transition and inner transition elements dominate the scene in

the present day coordination chemistry. Here again, the 3d transition metals

have been the most extensively studied for a variety of reasons. The first

transition series elements can have cations with incomplete 3d orbitals.

Generally, the d orbitals project well out to the periphery of the atoms and

ions, so that electrons occupying them are strongly influenced by the

surroundings of the ions and, in turn, are able to influence the environments

very significantly7•11·18.

3

A BRIEF ACCOUNT OF THE OXIDATION STATES, ELECTRONIC

STRUCTURE, STEREOCHEMISTRY AND MAGNETIC PROPERTIES OF

THE COMPLEXES OF IRON, MANGANESE AND CHROMIUM ARE

DESCRIBED BELOW.

Iron

Although a number of oxidations states from -2 to +6 are known for

iron, the most important and common are +2 and +3. Majority of the Fe (II)

complexes are octahedral. Tetrahedral coordination of Fe (II) is comparatively

rare. The [FeCI4] 2- ion exists in salts with several large cations. Sulphur

coordinated complexes of protein rubredoxin and phosphine oxide complexes

of the type Fe (Ph3POhX2 or [Fe(Ph3PO)4f+ are few examples for the Fe (II)

tetrahedral geometry19-21. A moderate number of pentacoordinate complexes

are also known. Those with tripod ligands usually have distorted trigonal

bipyramidal structure. Examples are bromo tris (2-dimethylaminoethyl) amine

complex, [FeMe6 (tren) Brr and tris (2-diphenylphosphinophenyl) phosphine

complexes, [Fe (np3) Xr (X= CI ., Br ., I - or N03 "). The 1,8 - naphthyridine

and crown ether complexes of Fe (II) are found to have dodecahedral

structure22,23.

The ground state of Fe (II) has d6configuration and the ground term for

the free ion is 50. In the presence of an octahedral ligand field, it is split into

5T2g and 5Eg. The orbitally triply degenerate T2g is the ground state. There are

no other quintet states present and therefore only one spin allowed transition

for octahedral iron (II) complexes corresponding to 5T2g -7 5Eg is possible. It

occurs in the visible or near-infrared region and is broad or sometimes split

due to Jahn-Teller effect in the excited state, which derives from a t2g3 eg3

configuration. Magnetic moments for high-spin octahedral Fe (II) complexes

are -5.2 BM in magnetically dilute compounds.

All tetrahedral Fe (II) complexes are high-spin and spin allowed

transition 5E -7 5T2 appears around 4000 cm-1. The magnetic moments of

tetrahedral complexes of Fe (II) are normally in the range 5.0-5.2 BM.

4

For Fe (II) quite strong ligand fields are required to form low-spin

octahedral complexes. However a number of low-spin complexes,

such as [Fe (CN) 6) 4·, [Fe(CNR)6] 2+, [Fe(phen)2(CN)2 ) and [Fe(phen)3]2+

(phen = 1, 10-phenanthroline) are known. The complexes of the type

[Fe(phen)2X2] are high-spin but when X = SCN or SeCN a spin state

crossover situation occurs. The magnetic moment of these complexes are

temperature dependent and ranges from -5.1 BM at 300K to -1.5 BM

at ;:;150K. A number of crossover cases have been studied in detail24-29

.

When the symmetry of the octahedral complex is strictly Oh, there can

be four or no unpaired electrons for a d6 system. But when the symmetry

changes from Oh to 04h a ground state with two unpaired electron is also

possible. Best documented examples are complexes of the type [Fe(LL)2ox]

and [Fe(LL)2 mal], where LL is a bidentate ligand such as 2, 2'-bipyridine or

1, 10-phenanthroline and 'ox' and 'mal' represent oxalate and maleato ions.

The magnetic susceptibilities of these Fe (II) complexes obey the Curie-Weiss

law over a wide range of temperature. The magnetic moment is found to be

-3.90 BM30• In a four-coordinate complex such as phthalocyanin iron (II), the

tetragonal distortion is extreme and the complex may be considered strictly as

square planar31.

Fe (Ill) forms a large number of complexes and majority of them are

octahedral. Crystalline salts such as K3FeF6 have octahedral FeF63

- unit32 and

complexes formed by phosphate ions, oxalates, glycerol and sugars of

iron (Ill) have also octahedral geometry. Iron (Ill) has a lesser tendency to

form tetrahedral complexes than iron (II). An example for tetrahedral complex

of iron (Ill) is [FeCl4) ·.

Though iron (111) isoelectronic with manganese (II), it is difficult to have

any spectra-structure correlation in the case of Fe (Ill) complexes. This is

because of the much greater tendency of the trivalent ion to have charge­

transfer bands in the near ultra-violet region, which have sufficiently strong

low-energy wings in the visible region to obscure almost completely the very

5

weak, spin-forbidden d-d bands. However, the spectral features of Fe (Ill) ions

in octahedral surroundings are well in accord with the theoretical predictions.

Iron (111), like manganese (II), is high-spin in almost all of its

complexes except those with strongest ligands, such as cyanide ions,

1, 10-phenanthroline or bipyridine and tris chelates with imine nitrogen atoms

as donors. Iron (Ill) with d5 configuration has ground state 6A1 9 in an

octahedral weak field arising out of the free ion term 68. This is the only sextet

state present and it has no orbital angular momentum. Therefore the

magnetic moments of these complexes are very close to the spin only value of

5.92 BM. Low-spin complexes with a ground state configuration of t2/, usually

have considerable orbital contribution to their magnetic moments. At

room temperature the magnetic moments of low-spin Fe (Ill) complexes are

-2.3 BM and this is found to be temperature dependent.

Five coordinate complexes of Fe (Ill) can be high-spin or low-spin

depending on the nature of the ligands. The oxo-bridged binuclear complexes

of the type [Fe(salen)Clfa, (salen = bis- salicylaldehydeethylenediimine), are

important high-spin complexes with marked antiferromagnetic coupling

between the iron atoms33. The monohalogeno bis - (dithiocarbamato) iron (Ill)

complexes, Fe (S2CNR)2 X (X=CI", Br" or I"), are reported to show magnetic

moment about 4.0 BM, which is very nearly equal to the spin only value

3.87 BM calculated for three unpaired of electrons. These molecules have a

very distorted square pyramidal geometry with halogen on the axial position.

Tris - (dithiocarbamato) and Schiff base complexes of Fe (111) are typical

examples for spin crossovers and high-spin-low-spin equilibria 34•35

.

Manganese

Although for manganese with electronic configuration 3d54s2, all

oxidation states from -3 to +7 are known, only Mn (II) and Mn (Ill) complexes

have been extensively studied. The divalent d5 state is the common and most

stable oxidation state. Mn (II) forms a number of high-spin complexes, which

lack any ligand field stabilization energy. The ground state term 68 of the free

6

Mn (II), ion, is not split in the ligand field and is transformed into 6A, 9 in the

octahedral field. In an octahedral field this configuration gives spin-forbidden

as well as parity-forbidden transitions. This accounts for the extremely pale

pink colour of such Mn (II) complexes. In tetrahedral fields, the transitions are

still spin-forbidden but no longer parity-forbidden and are 100 times stronger.

Therefore tetrahedral complexes of Mn (II) are pale yellow-green and the

colour is more intense than that of octahedral complexes. The high-spin d5

configuration gives essentially spin-only magnetic moments of 5.9 BM, which

is not temperature dependent.

At very high values of crystal field splitting energy, t29 5 configuration

gives rise to a doublet ground state. For manganese (11) the pairing energy is

high, and only a few low-spin complexes such as [Mn(CN)6]4 ·, [Mn(CN)5N0]3

·

and [Mn(CNR)5]2+ are known. Mn (II) has a 4A, 9 ground state in the square

planar dithiocarbamato complex Mn (S2CNEt2)2 36137

.

The ground term for the free Mn (Ill) ion is 5D. In the presence of an

octahedral field it split into 5E9 and 5T29. The ground state, 5E9 (t2/ e91) of an

octahedral Mn (Ill) is subjected to Jahn -Teller distortion. Considerable

elongation of two trans bonds has been observed in many Mn (Ill) complexes.

For example the distortion of spinel structure of Mn304 where Mn+2 ions are in

tetrahedral interstices and Mn+3 in octahedral interstices. Each of the Mn (Ill)

ion tends to distort its own octahedron and finally the entire lattice is distorted

from cubic to tetragonal.

For octahedral Mn (Ill) complexes only one spin-allowed absorption

band corresponds to 5E9 "7 5T29 is expected in the visible region. For the

complexes tris (oxalato) and tris (acetylacetonato) manganese (Ill) a broad

band appears around 20,000 cm·1 and the red or red-brown colour of high­

spin Mn (Ill) complexes are attributed to such absorption bands. The spectra

of some six coordinate Mn (Ill) complexes are difficult to interpret in all their

details, because both static and dynamic Jahn -Teller effects perturb the

simple picture based on Oh symmetry.

E

N

E

R

G

y

7

Free ion Cubic field (O

h)

Tetragonal field

(D4h)

Energy levels for high spin d4 system

Low-spin complexes of manganese (Ill) are also known to exist, but

limited in number. [Mn(CN)6]3- and dimethylaminotroponiminato

manganese (Ill) complexes are few examples.

A moderate number of five coordinate Mn (Ill) complexes are also

known38• A complex of unique interest is Mnl3(PMe3)2 , which is formed by the

oxidation of Mn'2 in excess of PMe339• The square pyramidal complexes,

[Mn(salen)X] where X= OAc ·, Cl", Br· or I ·, are found to have five coordinate

structure40•

41. The anionic part [MnCls]"2 in the bipyridine complex salt [bipyH2]

MnCl5 is also believed to contain five-coordinate Mn (Ill) with a square

pyramidal geometry42. A seven coordinate trihydride manganese (Ill)

complex, MnH3 (dmpe)2 has also been reported43.

Chromium

Though a number of oxidation states are known for chromium, the most

stable and generally important are +2 and +3. In an octahedral environment

both high-spin and low-spin electron distributions, t2/e9

1 and t2/e9 °, are

possible. The high-spin octahedral complexes are more common and show

marked tetragonal distortion owing to the Jahn-Teller effect. The compound

8

Cr2Fs contains both Cr (II) and Cr (III) ions in octahedral environments, but the

octahedra about the Cr (II) ions are highly distorted. These high-spin

complexes obey Curie-Weiss law and the magnetic moments are found to be

- 4.95 BM. The low-spin octahedral complexes require strong ligand

fields. The complexes such as [Cr(CN)st, [Cr(bipYhf+ and [Cr(diars)X2]

(diars = o-phenylenebisdimethylarsine and X= cr, B( or n are few low-spin

octahedral complexes of Cr (II). Magnetic moments of Cr (II) low-spin

complexes are found to be in the range 3.2-3.3 BM.

There are numerous high-spin four coordinate square complexes. The

pyrazolyl complex Cr[R2BPz2] 2 with R = H or Et44 and the acetylacetonato

complex, Cr(acac)2 are few examples of it. The tetraphenylporphyrin complex,

which takes up two pyridine ligands [Cr(porphy) PY2], is found to be low-spin.

A series of Schiff base complexes are also reported4s.

Five- coordinate complexes usually have distorted trigonal bipyramidal

structure as illustrated by complexes with tripod ligands. Examples are

[Cr(Mestren)Brt, [Mestren = tris (2-dimethylaminoethyl)amine] and [Cr(Pn3)W

(Pn = Propylene-diamine). With the bulky ligand Me3CO·, an unusual

T-shaped three coordinate complex species is found in

Cr(OCMe3)2.LiCI(THF)246.

The term symbol for the free Cr (III) ion is 4F. In an octahedral field it

split into 4A29, 4T2g and 4T1g. Among the three states 4A29 state lies lowest in

energy. The electronic transitions to 4T19 (P) must also be considered. Three

spin allowed transitions are possible due to 4A2g-7 4T2g, 4A2g -7 4 T19 (F) and

4A2g-7 4T1g(P) transitions. In the case of regular octahedral hexaaqua ion

complex, [Cr(H20)s]3+, the bands are found at 17,400, 24,700 and 37,000cm-1.

The magnetic properties of the octahedral Cr (III) complexes usually

agree with the spin only value 3.88 BM47. The chromium (III) carboxylate

of the type, [Cr30 (02CR)6L3t1 ( L = H20 or pyridine ), is reported to

show magnetic moments about 3.2 BM. Such low values of ~eH due to

9

metal-metal interactions are possible for dimeric or polymeric complexes with

bridged groups4S-50.

Anionic complexes of Cr (III) are also common and are of the type

[CrX6]3-, where X may be F, cr, NCS-, or CN-. The oxalato complex [Cr(ox)s]3­

is an example for Cr (III) complexes of bidentate anions. Compounds of

formula KCrX4 and [PCI4] [CrCI4], contain CrX6 octahedra with some sharing

of X atoms51 .

Quite a few five-coordinate complexes are known for Cr (III) with

trigonal bipyramidal structure. The adduct CrCI3.2NMe3, provides an example

of Cr (III) having trigonal bipyramidal structure with axial amine groups. Halide

bridged complexes such as [CrCI3(PR3)2h have also been reported. Distorted

tetrahedral coordination, presumably due to extreme steric factors, is found in

the reported complex LLCr[OCH(CMe3)2]4THF, (THF = tetrahydrofuran) 52.

A summery of metal complexes derived from certain diamines and

amides is given below.

A BRIEF REVIEW OF METAL COMPLEXES WITH CERTAIN DIAMINES

AND AMIDES AS LIGANDS

Yoshida et al. in1974 reported the preparation and characterization

of N, N' - bis (1-acetonylethylidine) ethylenediamine (AEH2) complex

Eu (AEH2) Cb.Eu (AEH2h CI353.

Nasanen et al. in1974 reported the preparation of bis (N, N-dimethyl-1,

3- propanediamine) Copper (II) bromide. The magnetic susceptibility of the

compound obeys Currie-Weiss law at 90-300K54.

Mononuclear, binuclear and heteronuclear Cr(llI) chelates of

triethylenetetraamine hexaacetic acid (ttha) were isolated and magnetic

measurements were also carried out by Smith et al. in 197555.

Synthesis and spin-state studies in solution of y-substituted tris

W- diketonato) iron (III) complexes and eight new magnetically anomalous

10

p - ketoimine iron (Ill) complexes containing hexadentate ligands derived from

triethylenetetraamine (trien) and various p-diketones were reported by

Dose et al. in 197656.

Narang et al. in 1976 reported the preparations and characterization of

copper (II) complexes of the compound Cu(en)2 D2, where en = ethylene­

diamine and HD = sulphonamide, viz., sulphathiazole, sulphapyridine,

sulphamerazine or sulphadiazine. The complexes were found to be planar

and paramagnetic and the sulphonamide molecules act as anions57.

Chin et al. in 1976 reported the preparation and some reactions of

diethylenetriamine palladium (II) - solvento complexes, [Pd(dien)L](CI04)2

(dien = diethylenetriamine, L= Me2S0, DMF, MeCN or H20)58.

Chicote et al. in 1977 obtained the mixed olefin platinum (0) complex of

maleic anhydride, [Pt (Cod) ma] where Cod = 1, 5 - cyclooctadiene and

ma = maleic anhydride59.

Studies of lanthanide complexes derived from N, N' bis

(2-aminoethyl) - 1, 3 - propanediamine were reported by Edward in 197760.

Circular dichroism studies of triethylenetetramine-N2, N3-diacetic acid

type Cobalt (111) and bicyclic -1, 3- diketone iron (Ill) and Copper (II) complexes

were reported by Michael in 197761.

Turpeinen Urho et al. in 1978 reported the crystal structure of the

nitrato bis (N-methyl -1, 3 - propanediamine) Copper(II) nitrate,

[Cu(C14H12N2)2N03]N03. The compound crystallized in triclinic space group62.

Buddha et al. in 1978 reported the ESR study of Cu (II) complex,

[Cu(trien)(SCN)] NCS (trien = triethylenetetraamine) in EtOH, MeOH, DMF,

HOCH2-CH20H and aqueous solution frozen at 77K, showed that the square

pyramidal symmetry.of the CuN4S chromophore in the solid state is preserved

in these solvents and in the frozen phase yields four hyperfine lines for the

cu+2 ion for all solvents except H20. The spectrum in H20 at 77K is explained

in terms of poor glass-forming ability63.

11

Sinn et al. in 1978 determined the structural, magnetic and mossbauer

properties of [Fe(acac)2(trien)]PF6 , [Fe(acac-Cl)2(trien)]PF6 ,

[Fe(sal)2(trien)]Cl2 .H20, and [Fe(sal)2(trien)]N03.H20, (trien = triethylenetri­

amine, acac = acetylacetonato, acac-CI = chloroacetylacetonato,

sal = slicylaldato). Hydrogen bonding was also discussed. Crystallographic

parameters of the monoclinic complexes were also reported. The fine

structural details for the compounds reveal significant differences in the metal

atom environments, which can be largely attributed to the differing spin

states64.

Duesler et al. in 1978 reported the crystal and molecular structure of the

mixed ethylene diamine (en), 1, 3- propanediamine (tn) complexes of Cr (Ill),

[Cr(tn) (en)2] Br3.H20 and [Cr(tn)2(en)]l3 .H2065.

A convenient preparation of the ligand ethylenediamine tetracetamide

(L) was described and a number of metal complexes of the general formula

MLCln. xH20 (M= divalent ions of Ca, Mn, Fe, Co, Ni, Cu, Zn, Mg, Ba, Cd and

Hg, and trivalent La) were prepared and characterized by Hay et al. in 197966 .

Syamal Arun et al. in 1979 synthesized and characterized a series of

new Co (Ill) complexes of general formulae [Co L (trien)]X3, L = tropolone,

biguanide, 2-guanidino benzimidazole, propylenediamine, triethylene­

tetraamine (trien). The complexes were found to be diamagnetic67.

Preti Carlo et al. in1979 reported the synthesis and characterization of

five coordinate bis (carbodithioato) tris (ethylenediamine) Nickel (II)

complexes68•

Bis (m-methylbenzoato) (1-3 - propanediamine) nickel (II) and

bis - (p-methylbenzoato) (1-3 - propanediamine) nickel (II) complexes were

reported by Klinga Martti in 1980. The crystals of the complexes were found

to be orthorhombic and monoclinic systems respectively. The Ni atom is

octahedrally coordinated with 4N from two propanediamines and two O atoms

from benzoato groups69.

12

Jeffery John et al. in 1980 reported the coordination chemistries of

N, N' - bis (o-diphenylphosphinobenzylidine) ethylenediamine (enP2) and

corresponding 1, 3 - propanediamine derivative (tnP2) was explored for

Ni, Cu and Ag and these results provide fundamental information on this novel

class of metal complexes70.

Crystal structure and spectroscopic properties of a polymer complex

between Cu (II), diethylenetriamine and ferrocyanide, (Cul)2Fe(CN)6.6H20

were reported by Oscar et al. in 1980. The structure consists of a CuLFe(CN)6

polymer linked by CN bridges. The spectroscopic properties of the

corresponding dimethyldiethylenetriamine complex were also determined71.

Isolation of all the five geometrical and conformational isomers of bis

(isothiocyanato) (triethylenetetramine) cobalt (Ill) complex, [Col(NCS)2t was

reported by Yukio et al. in 1981. Each isomer was identified from its chemical

properties, 13 NMR and absorption spectrum72 .

Syamal et al. in 1981, prepared and characterized new mixed ligand

complexes of Co (Ill) containing ethylenediamine (en), propylenediamine(Pn),

and some bidentate N N, 0 0 and N O donor ligands(L) (L= monoprotonated

biguanide, 2-picolylamine, triethylenediamine), [Co(en)(Pn)L]'3 and

[Co(en)(Pn)L 1 ]X2 (HL 1 = acetylacetone, quinaldinic acid, picolinic acid,

X = Cl, Br, I )73.

Synthesis and characterization of cyanobridged dinuclear complexes,

[L2FCr (µ-CN) M (CN)3], (L = ethylenediamine (en) or 1, 3 - propanediamine

(Pn), M = Ni, Pd, Pt) were reported in 1981 by Ribas et al. 74.

Preparation and characterization of triethylenetetramine complex of

molybdenum(V), [(trienH4)(MoOCls)2], [(MoOCl3)2 (trien)] and

[Mo0204C'2 (trien)] were reported by Su and Oh in 198275.

The crystal structure of the (-) bis (isothiocyanato) bis

(1, 3 - propanediamine) chromium (111) bis [µ - (+) tartarate(4-)]

bis(antimonite (Ill) dihydrate and its cobalt (Ill) analogue were reported by

13

Matsumoto et al. in 1982. Crystals of both complexes were of orthorhombic

system 76,

Preparation and study of copper (II) and nickel (II) with ethylenediamine

- N, N' - disuccinic acid were reported by Springer Vladimir et at. in 198377.

The overall stability constants of mixed ligand complexes formed by

lead (II) with ethylenediaminemalonate and propylenediaminemalonate at

298K were determined by Garg et al. in 198378.

The formation of complexes between palladium(ll) and

triethylenetetraamine hexaacetic acid (TIHA, H6L) was studied by measuring

H-ion concentration with a glass electrode, 1:1 and 2: 1 metal to ligand

complexes with different degree of protonation were observed and the

corresponding equilibrium constants were evaluated by Napoli Aldo in 198479•

The solid iron (III) complexes with N. N' - ethylenediamine disuccinic

acid were synthesized and characterized by ir spectra and thermogravimetry

by Mitrofanova et al. in 19848°.

Solid state and solution properties of N, N' - ethylene - bis

(salicylideneaminato) nitrato iron (III) and related complexes were reported by

Fanning et al. in 1985. The 57Fe mossbauer spectra and magnetic

susceptibilities of the complexes were comparable to similar data for the

tetraphenylporphyrin (HTPP) complex, Fe(TPP)02N03 which is monomeric

with a bidentate N03-.81

In 1985, Das and Roy prepared and characterized the complexes of the

type MLdNCXh, M = Co(lI) or Zn(II), X = 0, S, Se and

L = Propylenediamine or o-phenylene diamine. All NCX- were N bonded in

these octahedral complexes82.

Preparations and characterization of some unsymmetrical cis­

ethylenediamine N, N'-di-3-propionato cobalt (III) complexes were reported by

Radanovic et al. in 1985. The tetradentate ethylenediamine - N, N'­

dipropionate ligand prefers the unsymmetrical cis -configuration, suggesting

14

that the size of the carboxylate ring has a profound effect on the distribution of

geometrical isomers83.

Synthesis and characterization of antiferromagnetic chloro-bridged

binuclear iron (III) complex, [FeCIL](BPh)4, where H4L = N, N, N', N'-tetrakis

(3-salicylidineaminopropyl) ethylenediamine, were reported in 1985 by

Matsumoto et al. 84.

The stereochemistry of the Co (III) complexes of novel stereo specific

flexible quardridentate ligands such as N, N'-dimethylethylenediamine - N, N'­

di-u-propionic acid and N, N'-dimethylethylenediamine - N, N'-diacetic acid

were reported by Jun et al. in 198585.

Dagnall et al. in 1985 reported the 13C NMR study of the complexes

formed between Zn (II) and triethylenetetraamine. The spectra were studied

as a function of pH and the pH profiles for the exchanging systems were

analyzed by computer. Chemical shifts of the three non-equivalent C atoms

and stability constants of the complexes were determined86.

Thermal studies of 1, 2-propanediamine complexes of Zn (II) and Cd (II)

in solid phase where reported by Ghosh et al. in 1985. The zinc (II)

complexes were found to be more thermally stable than cadmium (II)

complexes. All these complexes were thermally less stable than those of

1, 2 - ethanediamine complexes87.

Bianchini and Logg in 1986 reported 2H NMR study of

chromium (III) complexes of ethylenediamine - N, N' - diacetate and

1,2 - propylenediamine -N, N, N', N' - tetraacetate as ligands88.

Structure of diethylenetriamine (imidazole) Copper(lI) perchlorate and

diethylenetriamine (1-ethylimidazole) Copper(ll) perchlorate were reported by

Miki et al. in 1986. The structures of both complexes were octahedral. The

complexes were found to be orthorhombic and monoclinic respectively89.

15

Preparation and crystal structure of an imidazolate-bridged polynuclear

complex, diethylenetriamine imidazolato copper perchlorate and its properties

in dimethyl sulphoxide solution were studied by Mosaaki Sato et al. in 198690.

The synthesis and characterization of isomeric (CoN5)3+ containing one,

two or three moles of ammonia, ethylenediamine (en), diethylenetriamine

(dien), triethylenetetraamine (trien) and tetraethylene- pentamine (tetren) were

reported by Yoshikawa et al. in 198691 .

A comparative synthetic and structural study of µ-oxo and µ-sulfido

derivatives of N, N'-ethylene bis (acetylacetoneiminato) iron(III) including the

parent complex, [Fe(acen)Py], were studied by Corazza et al. in 1987. These

complexes were found to have high-spin configurations and strongly

antiferromagnetic92.

The interaction of N, N'-ethylene bis (salicylideneimine), (H2salen) with

(NH4)2 Mo04 yielded Mo02(salen) with cis-dioxo structure was reported by

Gonzales and Nagaraja in 1987. The HNMR chemical shifts of azomethine

protons in the free ligand and the complex were compared to suggest the

bonding of the azomethane N to Mo02 group93.

Structure of the nitrato N, N'- ethylene bis (salicylidineiminato) iron (Ill)

dimers, a ferric complex with a unidentate nitrate ligand was reported in 1987

by Rasce et al.94.

Willet in 1987 reported the structure of the Ni(I I) complex

bis (2, 2°

- triaminotriethylamine N, N', N", N'") dinickel (II) tetraperchlorate. It

consists of pairs of octahedrally coordinated Ni+2 ions and isolated perchlorate

ions. Each 2, 2°

, 2°

' - triaminotriethylamine (trien) ligand occupies four

coordination sites on each Ni+2 ions, spanning a pair adjacent octahedral

faces. The trien ligand bridges between two-nickel ions with two N atoms

coordinating in a cis fashion to each nickel atoms to complete the

Ni coordination95.

16

Batyr et al. in 1987 reported the quantum

disproportionation of H20 2 in the presence

triethylenetetramine complexes96•

chemical study of the

of manganese (II)

The structure and absolute configuration of the triethylenetetramine

complexes of cobalt (III), [cis-u-Co(trien) (NOh]X. H20 where X = I or

CI, obtained as conglomerates when aqueous solutions of these species

crystallized either by evaporation at room temperature or cooled in a

refrigerator at _2°C were studied by Ivan Bernall and James Ctrullo in 198797,

The stabilities and thermodynamic properties of decadentate

triethylenetetramine hexaacetic acid complexes of the lanthanide (III) ions

were reported by Hsen et al. in 198798.

Guseinov et al. in 1987 reported the synthesis of a charge transfer 1:1

complex of maleic anhydride and 5-(bromoacetoxy methyl) norborn-2-ene

during polymerization99.

Copper (II) and nickel (II) complexes with N1, N4-bis (2,4-dinitrophenyl)

triethylenetetramine and the corresponding 2,4-diaminophenyl derivatives

were synthesized and characterized by Shukla et al. in 1987100.

Mixed ligand complexes of palladium (II) with diethylenetriamine and

other selected ligands were investigated by Shoukry et al. in 1988101 .

Multinuclear NMR of lanthanide (III) complex of diethylenetriamine

pentaacetate (DTPA) in the presence of Li as counter ion in aqueous solution

was studied by 13C, 170 and 6Li shift and relaxation measurements by Joop in

1988. The data show that the DTPA ligand bound octadentately via., the

3N atoms and the 5 carboxylates102.

Madhu et al. in 1988, reported the ESR spectra of copper, cadmium

and zinc complexes of triethylenetetraamine, [Cu(trien)NCS] BPh4,

[Cd(Cu) (trien)12] and [Zn(Cu) (trien) b] where BPh4 = tetraphenylborate103.

17

The synthesis and characterization of palladium(II) complexes with

triethylenetetramine hexaacetic acid were reported by Zheligovskaya et al.

in 1988104•

Cis - a - [Ru(bpy)(trien)](CI04)2 and cis - a - [Ru(Phen)(trien)](CI04)2

where bpy = 2.2°

-bipyridine, Phen = 1, 10- phenanthroline,

trien = triethylenetetramine, were prepared and characterized by Pasha 105

.

The formation of a 1 :1 charge transfer complex of maleic anhydride with

methylbenzene, benzene, isoprene and butadiene was reported by

Du et al. in 1988106 .

The hydrogen bonded complex, between an allyl carbonate group of

diethylene glycol bis (allylcarbonate) and maleic anhydride was synthesized by

Kucher et al. in 1988107.

Ratovskii et al. reported the complex formation of maleic anhydride with

vinyl esters of phenol and p - methoxyphenol and the complexes were studied

by ir and u.v spectroscopy and MO methods to obtain the information of

polymerization mechanisms 108.

Hu Shengzhi et al. in 1989, the synthesis and structure of diperchlorato

(diethylenetriamine)(imidazole) copper (II), [Cu(lmH) (dien) (CI04)2]. The Cu

atom was found to be in tetragonally distorted octahedral environment with

4+2 type coordination. The two-perchlorate groups were monodentate in the

axial positions 109.

Synthesis and characterization of Co(III) complexes containing

a- diamine and carbinolamine derived from a-aminomalonate and

ethylenediamine were reported by Kojima et al.110.

Buenzli · in 1988 reported to_e_s_ynthesis, X-ray and spectroscopic

investigation of europium (111) trinitrato complex [Eu(H2L) (N03)2] N03.

H2L=2:2 cyclo condensed product of 2,6 - diformyl - 4 - chlorophenol and

diethylenetriamine 111 .

18

Synthesis of ternary complexes of Cu (II) with diethylenetriamine and

their role in the promotion of hydrolysis of a-amino acid esters were studied by

Shoukry in 1988112.

The thermodynamic parameters of silver (I) complexes with

1,3-diaminopropane, 1, 2- diaminoethane and diethylenetriamine in DMSO at

25° C were reported by Cassol in 1989113.

Mukkala reported the synthesis and use of activated N - benzyl

derivatives of diethylenetriamine tetraacetic acid as alternative reagents for

labeling of antibodies with metal ions. A series of bifunctional chelating

agents, substituted benzyl derivatives of diethylenetriamine tetraacetic acids

were synthesized. The lanthanide Eu+2 complexes of these reagents were

used to label antibodies (lgG) 114.

The NMR spin-lattice relaxation method was used to study

complexation in the Fe (III) citric acid(H3L) - ethylenediamine disuccinic acid

(H4L) system as a function of pH at ionic strength 0.1 and 30°. Trunova et al.

also reported stability constants for the complexes in 1989115.

The synthesis and characterization by 13C NMR of some transition

metal complexes with hexadentate N, N, N, N, 0, 0 - chromophoric type

ligands like 1,9 - diamino - 3,7 - diazononane - 3,7 - diacetic acid (H2L)

and triethylenetetraamine - N', N" - diacetic acid (H2L1) were reported by

Khalifa in 1989116.

Photochemical synthesis and crystal structure of diaquo

(ethylenediaminemonosuccinato) nickel (II) dihydrate, [Ni(Edms)(H20)2].2H20

were reported by Suyarov et al. in 1989. The complex was found to be

octahedral with tetradentate Edms-2 and 2H20 molecules and belongs to

orthorhombic system117.

Mizuta et al. in 1989 reported a novel structure of spontaneously

resolved germanium (IV) complex with ethylenediamine acetate monoacetic

acid, [Ge(OH) (Hedta)]H20118.

19

Ospanov et al. synthesized (unithiol)(triethylenetetramine) rhodium (III)

chloride hydrate from the reaction between cis [RhCb(trien)] CI and sodium­

2,3- dimercapto propanesulfonate (NaH2L) in aqueous solution119.

Hendry et al. reported Lel20b and ob21el cage complexes based on

[Co(Pnh]3+, Pn = Propane -1,2 - diamine. The synthesis, resolution and

tentative identity were described of the 1 fac and 3 mer geometrical isomers of

the Lel2 ob cages, as well as the subsequent conversion to their ob21el

diastereoisomers120.

Jin et al. in 1989 reported the five coordinate complex, [Zn (dien)(OAc)]

CI04, dien = diethylenetriamine. The complex cation had a distorted trigonal

bipyramidal geometry121.

Konigs et al. in 1990 reported the amide oxygen coordinated

gadolinium complex with a new amide ligand, diethylenetriamine pentaacetic

acid. The most notable feature of the structure was coordination of two-amide

carbonyl 0 atom to gadolinium. The Gd coordination polyhedron was found to

be a 9-coordinate tricapped trigonal prism with sites occupied by the 3-amine

nitrogen, 3 carboxylate oxygen, 2 amide oxygen and a H20 molecule122.

Proton NMR study of the complexes of molybdenum (V) with

ethylenediamine disuccinic acid, [Mo03(HL)f and [Mo03H2Lf were reported

by Larchenko et al. in 1989. Both complexes were found to have an

unsymmetrical structure. The synthesis and properties of Mo(VI)

ethylenediamine disuccinate and ethylenediamine tetracetato complexes were

also reported123.

Study on the crystal structure (Hydrogen propylenediamine tetracetato)

antimony (III), and the structural chemistry and the possible mechanism of

antitumour action of the antimony complexes were also reported by Hu and

Lin in 1989124.

Synthesis, isolation and characterization of three isomers of Co (III)

20

complexes of ethylenediamine - N, N' - di - S - isobutyl acetic acid were

reported by Jun et al. in 1989125.

Synthesis and structure of mer-(diethylenetriamine) (4-hydroxybutyrato

phenanthroline) Co(lIl) diperchlorato were reported by Ilyukhin et al.

in 1990126.

The Raman spectra of Fe (III) complexes with edta were observed by

Kanamori et al. in 1990, for the purpose of elucidating the structure of the

complexes in solution127.

The dimeric complex which is formed in an alkali solution was

characterized as being a binuclear complex consisting of 2- quinquedentate

hexacoordinate Fe (III) moieties with a Fe - 0 - Fe bridging unit. The

molecular structure of the trans (05) isomer of ethylenediamine ­

N, N' - diacetato - N, N' - di - 3 - propionato) cobaltate (III), trans (05) ­

(Co eddda)", determined by x-ray analysis and its structural comparison with

same metal (III) complexes of related ligands were reported by Mizuta et al.

in 1990128.

Holz and Horrocks carried out spectroscopic characterisation of some

rare earth complexes of triethylenetetraamine hexaacetic acid in 1990129.

Ethylsalicylate and triethylenetetramine condensed and reacted with

Mn (OAch or Mn (OAch in methanol - in air aHord MnL.4H20, where

H4L = O-HOC6H4-CONH-(CH2)2-NH(CH2)2NHCOC6H40H-O, which has a

trans - cis - cis - Mn(IV) N2 (amine) N2 (amide) N2 (amide) 02(phenol)

coordination sphere 130.

The ESR studies on [Cu(trien)(en)Me4] (BPh4b and

[Cu(trien)(enEt2)](BPh4), where BPh4 = tetraphenylborate,

en = ethylenediamine and trien = triethylenetetraamine, by Madhu et al. in

1990 revealed the coordination behaviour, fluxional nature and N-alkylation

effects on metal ligand bonds131.

21

The synthesis, characterization and properties of some macrocycle

complexes MnLX2 (L = macrocycle derived from triethylenetetraamine (TETA)

and 2,6 - diformyl pyridine or 2-theonyltrifluoro acetone, X = I or PF6), ML1Z

(M=Co, Ni, L1 = macrocycle derived from TETA and acetylacetone, Z = SCN

or PF6) and CuL212 L2 = macrocyle derived from TETA and 2,6 - diacetyl

pyridine), were reported by Malik et al. in 1990132.

The magnetic and electrochemical properties of Fe (III) with salicylidene

ethylenediamine and salicylidene propylenediamine were studied by

Wang et al. in 1990. The effects of the ~-oxo bridging on the structure and

electrochemical properties also studied133.

Crystal and molecular structure of mixed ligands complex

(imidazole)(ethylenediamine monosuccinato) copper (II), [Cu(lm)(Edms)] was

reported by Suyarov et al. in 1990. The Cu atom has an elongated tetragonal

pyramidal coordination with the 0 atom of the diamine fragment, 2N atoms for

the ethylenediamine fragment and the imidazole N atom in the equatorial

plane. The 0 atom of the glycine fragment is in the axial position134.

Gogoi and Phukan in 1990, reported the synthesis and characterisation

of the Cr (III), Fe (III), Co (II), Ni (II) and Cu (II) complexes of the ligand

L = diethylene triamine bis (dithiocarbamate). The chromium and iron

complexes, [ML(H20)CI] were octahedral, whereas [CoL].2H20,[NiL] and

[Cull were square planar. The ESR spectral features indicate significant

distortion from ideal symmetry135.

Synthesis and characterization of some metal complexes of

ethylenediamine mono dithiocarbamate, ML2, where M=Cu+2,Ni+2, Co+2,

Fe+2, Mn+2

, Zn+2 Cd+2 and M'L3, M' = Co+3 or Fe+3 were reported by

Salam et al. in 1990136.

Napoli reported the synthesis and characterization of mixed complexes

between Cu(II), Cr(lll) and diethylenetriamine in 1991 137.

22

Geraldes et al. reported the structure and dynamics of lanthanide

complexes, Lnl.nH20, where Ln = La+3, Nd+3, Dy+3 or Pr+3, n=1-3. H3L= bis

(propylamide) of diethylenetriamine pentaacetic acid. The NMR shift and

relaxation measurements show that the complexes occur in 2:: 8 isomeric

forms138.

Sadhir in 1991 prepared a charge transfer complex from maleic

anhydride and cyclic compounds with electron deficient elements and used as

low-temperature curing agents for organic resins139

Dash et al. reported that the anation of ~ - is [Co(H20)(trien)]3+ by

malonate proceeded via two rate controlling steps which were independent of

malonate140.

Oliver et al. reported the absolute configuration of (-)-cis-~- carbamato

(triethylenetetraamine) Cobalt (III) perchlorate monohydrate. This complex

was found to be monoclinic crystalline structure141.

Pasha in 1991 reported the isolation and characterization of cis-u­

salicylato (triethylenetetraamine) cobalt (III) chloride and its isomer by means

of both analytical and spectroscopic methods. The chloride anation of cis-u­

[RuCI(H20) (trien)f+, where trien = triethylenetetramine, has been studied

spectroscopically142.

Synthesis and characterization of the chelates of aluminum, gallium and

indium with 1, 2 - propylenediamine tetraacetic acid were reported by

Karweer et al. . The 1,2 - propylenediamine tetraacetic acid functions as a

pentadentate in H.AI.X .2H20 and hexa dentate ligand in K.AI.X .2H20 143.

Shin et al. synthesized triethylenetetraamine chelate resin by the

reaction of bis (salicylideneiminate) triethylenetetramine and chloromethylated

polystyrene resin. The complex formation constants were found to be in the

order of Cu(III) > Ni(lI) > Pb(ll) > Cd(lI) > Zn(lI) > Co(lI)144.

23

In 1991, Bezrukavnikova has studied the crystal structure of diamine

(1-diethylenetriamine monoacetato) Cobalt (II) perchlorate monohydrate145.

Sakagami et al. in 1992 reported, hexadentate, ethylenediamine

tetraacetate - like N, N, N', N' - tetra propionate (edtp), S-propane-1, 3 ­

diamine - N, N, N', N'- tetra propionate [(S) pdtp], and (1 S, 2S)-trans­

cyclohexane 1, 2 - diamine - N, N, N', N'- tetrapropionate (SS-cydtp) ligands to

synthesize novel diastereoisomers of chromium (III), which were characterized

by 2H NMR and CD spectra146.

Sakabe and Ogura reported the infrared spectral identification of

isomers of dicyano - bis - (propylenediamine) chromium (III) chloride and

related complexes147.

Pavloskii et al. in 1992, synthesized and characterized the mixed ligand

cobalt (III) complexes with triethylenetetramine and anthranilic or picolinic

acids, (Co(trien)L)(CI04h where trine = triethylenetetramine and

HL =anthranilic acid or picolinic acid148.

Kovaleva et al. studied the structural features of transition metal

complexes, derived from ethylenediamine - N, N' - disuccinic acid

in 1992149,

Preparation and characterization of two geometrical isomers of the

aqua (ethylenediamine-N, N, N'-tri-3-propionatopropionic acid) chromium (III)

complex, [Cr (Hedtp)(H20)).5H20, (H4edtp = ethylenediamine -N, N, N', N'­

tetra-3-propionic acid), were reported by Sakagami and Kaizaki in 1992. The

geometrical structure of one isomer was assigned to cis - equatorial by x-ray

crystal data and another isomer was assigned to trans equatorial on the basis

of 2H NMR and magnetic CD Spectra150.

Kanayana et al. in 1992, prepared an aromatic diamide by treating a

mixture of 2,4 - and 4,6 - diamine, 3, 5 - diethyl toluene with maleic anhydride

in toluene and then treated with p-Me C6H4S03H at 1120 C to give bis

maleimide151.

24

The photo oxidation of N, N, N', N' tetramethyl

- p - phenylenediamine by maleic anhydride was studied by a time resolved

ESR method by Honmer et al. 152.

Takagi and Musutoshi prepared a bis maleimide by treating maleic

anhydride and di (aminomethyl) norborane (2: 1) in DMF at 60° C, which was

again heated in DMF at 90-95° C in the presence of polyphosphoric acid to

give norborane bis methyl maleimide153.

Begum et al. in 1992, reported macrocycle metal complexes of the type

(MLt2 where M= Mn, Co, Ni or Zn, L = cyclo condensation product of 2,6 ­

diformylpyridine and TETA, prepared by template synthesis and characterized

by physicochemical methods154.

Keramidas and Rentzeperis in 1992, reported monoclinic crystal

structure for triethylenetetramine copper(lI) fluorophosphates,

[Cu(trien)(PFa)a]. The coordination around central 'Cu' atom was found to be

octahedral with the 'Cu' atom 0.096 AO below the equatorial plane of four N

atoms of the ligand molecule. Two F atoms of the fluorophosphate groups

occupied the remaining positions of the octahedra155.

Kim et al. reported the synthesis and characterisation by ESR

spectroscopy of a paramagnetic complex, Re(CO)4L2, L = 2, 3 - bis ­

(diphenylphosphino) maleic anhydride156.

Dash et al. reported the base hydrolysis of P2-cis-[Co(trien)(Hbzm)CI]2+,

trine = triethylenetetramine and Hbzm = benzimidazole. The base hydrolysis

obeyed the rate law, which includes both Hbzm and bzm forms of the complex

and the equilibrium constant for the OH" promoted of the benzimidazolate

species form parent complex157.

The synthesis, characterization and thermal behaviour of

triethylenetetra ammonium isopolyoxovanadates, (H4 trien) (V03k2H20, H4

trien (V1Q02S)2.7H20 and H4trien (M2V1Q02S).4H20 were reported by

Roman et al. in 1992158.

25

Muir and Torres in 1992 carried out the ligand field photolysis of the

dichloro complexes [Rh(Me trien)CI2] X, X = CI or CI04, n = 0, 2, 3,

Me trien = TETA derivative and the quantum yields for cr release were

determined159.

Nakashio in 1992 reported the use of ethylenediaminediacetamides and

diethylenetriamineacetamides as complexing agents 160.

andsynthesis

mono and bis

as potential DNA and RNA

reported the

and chiral

1992inStephenandRushdi

characterization of a series of chiral

(diethylenetriamine) platinum (II) complexes

d ' d 161structure probes an anti-cancer rugs .

Davidovich in 1992 studied the characteristics of complexes

synthesized from diethylenetriamine with zirconium and Hafnium162,

Bonding of Rhenium (V) to diethylenetriamine pentaacetic functional

groups of a polymethylacrylate support was reported by Hoskovcova163.

Frommer in 1992, reported the synthesis and

characterization of 9 - methylguanine (9-MeGH) complex, mer - trans ­

[(dien) t(OH)2(9-MeGH)] (CI04k2H20164.

Shkol' nikova et al. in 1992, reported the preparation, crystal and

molecular structure of (N, N'-bis (2-carbamoyl ethyl) ethylenediamine- N, N'­

diacetato) Copper (I). The copper atoms were found to have a tetragonal

bipyramidal structure, axial positions of which were occupied by the 0 atom of

the propionamide group and a bridging 0 atom of the propionamide group

from a neighboring molecule165.

Polarographic study of mixed ligand complexes of cadmium (II) with

1,3- propylenediamine and some dibasic acids like adipic, malonic or succinic

acids was reported by Jain et al. in 1992166.

In 1993, Balaswamy et al. reported the synthesis and characterisation

of few complexes of Co (II), Ni (II), Cu (II) and Pd (II) with a tetradentate ligand

26

N, N'· ethylene . bis (3-carboxypropenamide) and a bidentate ligand

benz-(5,6) - 2 - carboxy-methyl -1 ,3,4-thiolactum167.

Siddiqi et al. in 1993, reported the synthesis, characterization and

reactivity of new heterobimetallic complexes of the type [Cu(TETA)CI2MCI2],

M= Si, Ge, Sn, Ti or Zr, TETAH2 = triethylenetetramine and

[Cu(TETA)CbSnPh2]. Cu ( TETAH2 ) CI2 was found to be square planar and

ionic, while [Cu(TETA)Cb MCI2] had an octahedral environment around the

Cu(ll) ion168.

The synthesis and characterization of mononuclear and binuclear

iron (III) complexes of the ligand N, N'· bis (2 - pyridylmethyl) ethane - 1, 2 ­

diamine (bis-picen) were described by Arulsamy et al. in 1993. The structures

of monomeric [Fe(bis- picen)CI2] CI04 and [Fe (bis-picen)CI2]CI were

determined from 3-dimensional crystallographic data169.

Mixed complexes of Pd (II) and Cr (III) with triethylenetetraamine

pentaacetic acid (DTPA) were studied at 20° in constant ionic medium

1.0 mol / dm3 (NaCI04) by using a glass and a stationary amalgam electrode

were reported by Bel Castro and Napoli in 199317°.Some transitional metal complexes [NiL(SCNh]' [NiL(H20h]X2, X= CI or

CI04 , Cd2LX, X = (N03)4, (S04 h or (CI)4 , ZnL(SCN)2, Zn2LX,

X = (S04)2 or (CI)4, [CrLX2]X, X = I or SCN and [CoL(SCN)](SCN).H20 were

isolated from the reaction of triethylnetetramine(L) with appropriate metal salt

solutions by Ahmed et al. in 1993171 .

Ivan et al. reported the crystallization behaviour of cis- [Co(en)2 (N02h ]

Br and cis - a - [Co(trien)N02] N03 .1/3 H20 where en= ethylenediamine and

trine = triethylenetetramine 172.

CassoI in 1993 reported the thermodynamic parameters of the

complexation of uranyl (IV) by diethylenetriamine in DMSO. The changes in

free energy, enthalpy and entropy for the complex formation reactions

between uranyl (IV) ion and diethylenetetramine in DMSO were determined173.

27

Manzar and Hussain reported the photometric method for the

quantitative determination of natural and ring-substituted indoles by

complexing with maleic anhydride. The coloured complex exhibits absorbance

maximum in the region 490-530 nm174.

Xu reported the structures of mixed ligand copper (II) complexes,

(diethylenetriamine) (ethylenediamine) Cu (II) diperchlorate 175.

Matsuyama Hidento in 1993 reported the potentiometric and

colourimetric data for the complexation of lanthanide (III) cations by the neutral

N-donor ligand diethylenetriamine in ionic medium and is anhydrous DMSO

at 250C176.

Aqra et al. in 1994 reported that the condensation of

triethylenetetramine and di-Et oxalate in the presence of divalent hydrated

transition metal chlorides (Mn+2, Co+2, Ni+2 or Cu+2) and ZnCI2 in the absence

of methanol (1: 1:1) yields ionic 12 - membered macrocyclic complexes. Two

H20 molecules were bound to the central metal ion Mn+2 ,Co+2, Ni+2 or Cu+2

resulting in an octahedral environment while Zn+2 maintains a tetrahedral

geometry being free from H20177

.

Han et al. in 1994 reported the synthesis and antitumour activity of

polyanion platinum complexes containing alicylic amines, like

diethylenetriamine as ligands. Polyanion platinum (II) complexes were

synthesized by reSUlting hydrolyzed maleic anhydride alternating copolymers

with cis - platinum amine complexes178.

Su Chang in 1994, synthesized and characterized the

diethylenetriamine copper (II) complexes of the type [Cu(dien) L (anion)2],

L= imidazole, 2-methylimidazole, 4-methylimidazole, pyridine and ammonia

and anion=BF4-or CI04-179

Binglin in 1994 reported the preparation of some polymeric

diethylenetriamine copper (II) complexes supported by porous cross-linked

poly (methylacrylate) as adsorbents for urea180.

28

Ganesh and Krishnan reported the preparation of complexes of Cu (II),

Co (II), Ni (II) and Fe (II) with the ligand obtained by the condensation of

4,4' - diaminodiphenyl-sulphone with maleic anhydride181.

Sekizaki et al. in 1994 reported the preparation and characterization of

the various isomers of [Co(Opa)(trien)]CI. nH 20 were H20pa = 2-hydroxy

phenyl acetic acid and trien = triethylenetetraamine182.

Masuda et al. reported the crystal structure of cis - ~ carbonato

(S, S - triethylenetetramine) cobalt (III) perchlorate. The complex was found

to be monoclinic and tetradentate triethylenetetraamine was linked to the

cobalt atom in cis - ~ configuration and the carbonato anion coordinated to the

metal atom as bidentate ligand183.

Jin et al. in 1994 reported the synthesis and crystal structure of

copper (II) complex of triethylenetetramine hexaacetic acid. The Cu (II) ion

was found to be five coordinated to form a square pyramid structure184.

Vaselinovic Dragan in 1995 studied the structural details of Cu (II)

complex of 1,3- propanediamine - N, N' - diacetic -N, N' -di - 3 - propionic

acid185.

In 1995, Song Rui-Fang studied the dynamic nuclear magnetic

resonance of In (III) and Y (III) - 1,2 - propanediamine tetraacetic acid186.

Synthesis, structure and antitumour properties of a novel complex

formed by ruthenium (III) with the sesquestering ligand 1, 2 ­

propylenediamine tetraacetic acid (PDTA) were reported by Vilaplana et al. in

1995. The structure of the monomeric complex [Ru(H 2LCI2]H.H20

(H4L=PDTA) studied by X-ray diffraction, shows an almost symmetrical

octahedral geometry around the metal ion, with two chlorine atoms in a cis

configuration. The antitumour activities against a variety of murine and human

cancers were reported187.

Synthesis and magnetic study of four novel trinuclear Cu (II)

complexes, [Cu(CHT ebo)(CuL)2] (CI04)2 where CH 3-ebo denotes

29

1,2 - propylene bis - (oxamido) and L= 1,10 - phenanathroline (phen),

5 - nitro 1,10 - phenanthroline (N02-phen), 2,2'-bipyridyl(bpy) or 4,4'-dimethyl

-2,2' - bipyridyl (Me2bpy) were reported by Miao et al. in 1995188.

Oonuma et al. in 1995 reported the preparation of bis maleimide

derivatives by the reaction of diamines with maleic anhydride followed by cyclo

condensation of the maleiamic acid derivatives in the presence of an acid

catalyst189.

Teresa in 1995 reported the study of the stabilization of

tetracyanoquinodimethane (TCNQ) anion radical with diamine and triamine

complexes of nickel and copper. The reactivity of organic acceptor 7, 7, 8, 8,­

tetracyanoquinodimethane in its neutral or anionic radical forms with

[M(enh]2+, [M(dienh]2+ was also studied19o.

The synthesis and properties of isomers of the salicylaldoximato

triethylenetetramine cobalt (III) complexes and crystal structure of

cis- 13 -(RS, SR) - [Co(salal)(trien)] CI. CH3COCH3. 2H20 were reported by

Umakoshi and Yamamoto in 1995191.

The synthesis, crystal structure and properties of a new imidazole

bridged copper - zinc heterobinuclear complex with triethylenetetramine (trien)

were described by Mao et al. in 1995. The complexes were

[(trien) Cu(lm) Cu(trien)] (CI04h H20 and [(trien) Cu(lm) Zn(trien)] (CI04hH20

where Him = Imidazole192.

Zhang et al. reported the study of triethylenetetramine hexaacetic acid

(TTHA) complexes with diamagnetic rare earth ions (La3+, y+3 and Lu+3) by

means of 1Hand 13C_ NMR spectroscopy in 1995. A symmetrical structural

model was suggested for La(TTHA) complex and an asymmetric model for

Y(TTHA) and LU(TTHA) complexes193.

Nanda prepared and characterized a new tetra nuclear macro cyclic

Ni (II) complex, [Ni4L(Il-OAc)2 (OAc)4(H20)4]. This was synthesised by the

30

condensation of 2,6 - diformyl - 4 - methylphenol and trien in presence of

Ni (II) perchlorate and excess of NaOAc194.

The preparation and characterization of the Cu(ll) complex,

[(N-3-methylsalicylidene)-N'-(imidazole-4-yl-methylene)-1 ,3-propanediamino]

copper (II) perchlorate was reported by Nozaki et al in 1995, The above

complex reacted with NaBH4 in DMF to give an electro neutral complex

containing B-N bond195.

Radanovic and Duran in 1995 synthesised and studied the Ni (II)

octahedral complex [Ni(1,3-pdda) (H20h], pdda = propanediamine - N, N' ­

diacetate196.

The structure and magnetic properties of azido-bridged Ni (II) complex

Ni(dpmnh N3(CI04) where dpmn = 2, 2 - dimethyl - 1, 3 - propanediamine

were studied by Yamashita et al. in 1995197.

Pillani et al. in 1996 synthesized the first crystallographically

characterized phosphine complex of copper (II) with (H2dppd),[H2 dppd =

N, N' - bis (2-diphenylphosphine) phenyl propane 1,3-diamine]198.

The 89y chem-shifts and 15N NMR coupling constants in aqueous

solution of three yttrium complexes of polyamino carboxylic acids, KY(EDTA),

K2Y(DTPA) and K3Y(TIHA) where EDTA = ethylenediaminetetracetic acid,

DTPA =diethylenetriamine pentaacetic acid and TIHA = triethylenetetramine

hexa acetic acid were measured by Lee in 1996199,

Asokan in 1996 synthesized and characterized a binuclear Cu(lI)

complex using a ligand derived from the condensation of 1,3 - aminopropane

and 2,6 - diformyl -4 -methylphenol2oo .

Abaet E1 - Nour in 1996 reported the static permitting and dielectric

relaxation study of complex formation in dilute solutions of maleic anhydride or

one of its derivative plus methylacrylate or styrene201 .

31

Prelesnik in 1996 prepared and determined the molecular structure of

trans-(Os) isomer of dihydrogen(1,3-propanediamine-N,N') diaceto-

N,N'-di-3-peropionato) copper (II) complex202 .

Diethylenetriamine (imidazole) (thiocyanato) copper (II) perchlorate was

prepared by a two-step process. Cu ion coordinated in a trigonal bipyramidal

arrangement by two primary N atoms of N(2-aminoethyl)-1, 2-ethylenediamine

(diethylenetriamine) and one N atom of thiocyanate in equatorial positions and

by the aromatic N atom of imidazole and the secondary N atom of

diethylenetriamine in axial position were reported by the Hu et al. in 1997203.

Sundberg in 1997 investigated the conformation and flexibility of the

di(1,3-diaminopropane) copper(lI) cation. Also, then determined the structure

of trans-diaquo- bis (1,3 - diaminopropane-N,N' ) Copper (II), trans-di­

(orthophthalato) bis (1,3 - diaminopropane-N,N') cuprate (II) monohydrate

complexes204.

Hu et al. in 1997 reported the preparation and studies on the

antitumour activity of antimony (III) triaminocarboxylic complexes. The

structures of the prepared complexes, NH4 [Sb(Hdtpa)].H20 and

Na [Sb(Hdtpa)] 4.5H20, where Hdtpa = diethylenetriaminepentaacetic acid,

were also determined by single crystal X-ray studies 205.

Xie Bin in 1997, reported the preparation and spectroscopic

studies of TCNO salts of copper, Cu(Pn)2 (TCNO)n, where n = 2 or 3,

Pn =Propylenediamine and rCNO =7, 7, 7, 8 - tetracyanoquinodimethane206 .

Esquor Albert in 1997 prepared and they determined the structure of

trinuclear [Ni2(/J-C03)(dmpd)4(H20)] [Ni(dmpd)2 (H20)2] (CI04)4 .H20 from the

reaction of basic solution of Ni(CI04)2 and 2,2-dimethylpropane­

1,3 - diamine (dmpd) with atm. CO2. The three Ni atoms were found

to show octahedral coordination with three different environments,

[Ni(C03-O,01) (dmpdh], (NiC03-011 )(dppd)2 H20 and Ni(dmpd)2 (H20k The

carbonate anion acted as a bridge between two Ni ions whereas the

32

[Ni(dmpdh (H20)2]2+ showed a moderately weak antiferromagnetic coupling

with a J value of -7.8 cm-1 207.

Kou et al. prepared a bimetallic complex [Cu(dienb (Fe(CN)6)h 6H20,

dien = diethylenetriamine and its crystal structure also determined. From

magnetic susceptibility measurements the complex was found to exhibit a

weak ferromagnetic interaction between Cu (II) and Fe (III) atoms208.

Wang et al. reported the relaxivity study and X-ray structure of a new

(amide) derivative of DTPA (diethylenetriamine - N, N, N', N", N"-pentaacetic ­

N, N"- bis (benzylamide)(DTPA-BBA) with Gd(III), [Gd(DTPA-BBA)]209 .

Priya Chandi in 1997 prepared a Cd(lI) dinuclear complex

[Cd(npda)4 (C03) H20] (CI04)2 .H20 from [Cd(npdab] (CI04)2, where npda =N'-isopropyl-2-methylpropane- 1,2- diamine This is the first example of a

Il-carbonate Cd(lI) diamine complex which was characterised by elemental

analysis, ir and crystal structure data 210.

The preparation of N-benzyl maleimide by treating maleic anhydride

with benzylamine using p-toluene sulphonic acid catalyst was reported by

Noda and Toshimitsu in 1997211 .

Kitagawa and Akio synthesised N, N- diisobutyl maleic monoamide by

the reaction of maleic anhydride with isobutylamine which was used in a

thermal recording layer formed on paper support212.

Wang et al. in 1997 reported the synthesis and crystal structure of the

potassium ytterbium complex with triethylenetetramine hexaacetic acid

(TTHA), [K3 Yb(TTHA) (H20)5]' In the complex the Yb+3 ion was find to be

coordinated by four N atom and five carboxyl '0' atoms of the TTHA6- ions.

The 'Yb+3, has a coordination number of '9' and has distorted mono capped

square antiprism structure213.

Robert et al. in 1997 published a paper in which he described the

synthesis of macrocyclic tetramide complexes by the reaction of

ethylenediamine or 1,3 - diaminopropane with malonic, succinic or glutaric

33

acids in methanol solution in presence of a metal (II) salt at room

temperature214.

Mondry and Starynowicz in 1997 reported the crystal structure and

absorption spectroscopy of Neodymium(III) complex with triethylenetetraamine

hexaacetic acid, Na2[Nd(TTHA)] 25NaCl04 7.6 H20. The crystals were found

to be monoclinic and the Nd(III) adopted a 1 O - coordinated geometry215.

Asokan and Varhese in 1998 synthesized and characterized a novel

polymer of a binuclear Ni (II) complex bridged by 1, 3 - diaminopropane216.

The solvatochromism and structure of acetyl acetonatocopper (II)

complexes with N, N'- dipropyl - N, N, N', N'-tetrapropyl and N, N- and N, N' -

diisopropyl ethylenediamine were reported by Miyamae et al. in 1998. The

crystal analysis showed that the perchlorates of N, N'-and N, N - diisopropyl

complexes were apparently 6 and 5- coordinated respectively in their

crystals217.

Zuran in 1998 reported the preparation and characterisation of square

pyramidal copper (II) complexes of linear tetradentate edda - type ligands

forming six- membered rings, [Cu(1,3-pdda) H20] [Cu(eddp)(H20)] 3.5 H20

and [Cu(1, 3 - pddp)H20]. pdda = 1, 3 - propanediamine - N, N' - diacetate

ion, eddp = ethylene diamine N, N' - di - 3 - propionate ion and pddp = 1,3 -

propanediamine, N, N' - di-3-propionate ion218.

Wei and Zhuo reported the synthesis of paramagnetic gadolinium,

ytterbium and iron chelate complexes with DTPA modified by P and O - amino

benzoic acid, DTPA = diethylenetriamine pentaacetic acid219.

Synthesis and structure using NMR spectroscopy of lanthanide of

N, N' -dimethyl -N, N' -diphenyl-3-oxopentanediamide (DMOPhOPDA) were

reported by Naritha et al. in 1998220.

Miodragovic et al. in 1998 synthesized and found out different

conformations of mixed cobalt (111) complexes with S - tyrosine and 1, 3 -

diaminopropane221.

34

Moore et al. in 1999 prepared [Ni(NCS)2 (H2N(CH2)3 NH2)2], an

octahedral complex of Ni (II) in which the thiocyanate ligands are bonded

through N in a cis-arrangement while the 1, 3 - propanediamine ligands are

N, N' - bidentate222 .

Radanovic et al. reported the hexadentate chromium (Ill) complexes

containing unsymmetrical edta-type ligands. Crystal structures of (-) - trans

(o5) Na[Cr(ed3ap)].3H20 and Na[Cr(eddadp)] .3H20 and CD spectra

correlation structural parameters of [Cr(edta- type)] complexes and their

octahedral distortion in relation to structure of the ligand were also reported223 .

Preparation and crystal structure of two polymorphs of

[Cu(tn)] [Ni(CN)4] where tn = 1, 3 - diaminopropane was described by

Cernak et al. in 2000, they also find the blue polymorph to be orthorhombic224 .

Dinuclear platinum complexes as cis - platin formed between

tetrachloropalatinate (II), [PtCl4f and triethylenetriamine or its derivatives,

Pt LC'2, L = triethylenetetramine or N, N1 - bis (2-dimethylaminoethyl) oxamide

were reported by Shaw Jiagin in 2000225.

Charles and Blackman in 2000 reported the synthesis and

characterization of the hypodentate complexes cis - [Co(en)2 (enH)(imH)]Br4,

[Co(NH3)s (enH)]Cl4, [Co(NH3)s(dienH2)]Cls, [Co(NH3)s(trenH3)]Cls.3H20 and

Co(tren)(NH3)(trenH3)]Cl6. 2H20 containing protonated monodentate

ethylenediamine(en), diethylenetriamine(dien) and tris (2-aminoethyl)

amine(tren)226.

Mondal Nizhuman et al. in 2000 reported the synthesis and

characterisation by single crystal x-ray diffraction of four new polymeric

complexes [Cd(dmen)(SCN)2]n, [Cd(deen)(SCN)2]n , [Cd(dmen)(N3)2]n and

[Cd(deen) (N3)2]n where dmen = N, N - dimethyl ethylenediamine and

deen = diethylene ethylenediamine227.

Synthesis and structure determination of seven coordinate,

K[l11 1 (Hdtpa)]3.5H20, H5dtpa = diethylenetriamine pentaacetic acid were

35

reported by Wang Jun et al. in 2000. Its crystal structure was determined by

single crystal X-ray analysis228.

Trifunovic Seeko et al. in 2000 reported the synthesis of new Mn (II)

complexes with ethylenediamine - N, N, N', N'-tetra -3-propionate (edtp) and

(1,2-propanediamine, N, N, N', N'-tetraacetate (1,2 - pdta). The complexes

were characterized by elemental analysis and ir spectroscopy and magnetic

measurements. The structure of [Mn(H21, 2- pdta)(H20)] 3H20 was

determined by the single crystal x-ray diffraction technique. The complex

crystallizes in monoclinic space group229.

Brezina Frantisek et al. in 1999 reported two novel binuclear complexes

of Ni (II) with hydroxide bridges, [Ni2L2(0H)2](CI04)2. L = triethylenetetramine

(TTA), tris (2-aminoethylamine)(TAA), were prepared and characterized by

spectroscopic and magnetic methods 230.

Sakagami et al. in 2000 reported the synthesis and structural

characterization of several new pyrazolato-3,5-dicarboxylato(pzdc) bridged

dinuclear chromate (Ill) complexes containing linear tetra dentate 0-N-N-O

type ligands like ethylenediamine -N, N' - dipropionate ( eddp )231 .

Synthesis and characterization of new metal vanadate complex

Cu(tn)2 (V03)2, where tn = 1, 3 - diaminopropane, were reported by

Lin B-Z et al. in 2000232•

The crystal structures of hydrates of gadolinium diethylenetriamine

pentaacetic acid bis (methylamide) (gadodiamide I and Ill) were determined by

X-ray diffraction technique by Aukrust et al. in 2001233 .

Radanovic et al. in 2001 reported the synthesis and x-ray crystal study

of magnesium (1,3-propanediamine tetraacetato) nickel (11) octahydrate

complex, Mg[Ni(1, 3 - pdta)]. 8H20, where 1, 3 pdta = 1, 3 - propanediamine

tetraacetate ion234.

36

Wang Jun et al. in 2000 carried out the synthesis and structural

determination of nine coordinate Y(III) complex, K2 [Y111(dtpa)H20] .7H20.

where dtpa = di ethylene triamine pentaacetate235•

Zhu Hai et al. in 2001 reported the synthesis and characterization of

two µ2-terephthalate (tp) bridged complexes, [Cu2(tp)(pren)4](CI04)2,

(pren = 1,3- diaminopropane) and [Ni2(tp)2 (pren)4(Him)2], (Him =

i m idazole )236.

Zhang et al. in 2001 carried out the synthesis and structural

determination of [Cu (C4H13N3) H20 (4,4'-Hbpy)].S04 . N03 (C4H13N3 =

diethylenetriamine. X-ray diffraction studies showed that the crystal system is

orthorhombic and 4,4'- bpy is monoprotonated 237.

Shen Liang et al. in 2002 reported the synthesis and crystal structure of

[Ni(dine)2]2 [Mn(NCS)5].H20 (diene = diethylenetriamine). The single crystal

X-ray diffraction studies showed that the system is monoclinic238.

John Caroline and Abdul Malik in 2002 reported the synthesis and

structural characterization of metal-saccharinate complexes, [M(dien)2]

2(sac).H20 (M = Ni(II), Cu(II), Zn(II), dien = diethylenetriamine ,C4H13N3 ,

sac = saccharinate, C1H4N03S") and [Cd(dien)2]2(sac). The Ni(II), Cu(II) and

Zn(II) complexes are isostructural and belong to the monoclinic while the

Cd (II) complex crystallizes in the triclinic system. In each case, two tridentate

dien ligands are bonded with the metal in a distorted octahedral arrangement

and the saccharin anions remain out side the coordination sphere but

participate in extensive hydrogen bonding net work239.

Mikael et al. in 2002 reported the preparation and characterization of a

new complex of Tl (Ill) with the N donor ligand diethylenetriamine (dien),

[Tl(dien)2 ] (CI04)3 . The crystal structure of the complex reported as u - facial

geometry, where the coordination environment around Tl is described as

distorted trigonal prism 240.