g bh evul can catalytic reaction guide
TRANSCRIPT
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HETEROGENEOUS REACTION CHEMISTRY
CONTENTS
0 HETEROGENEOUS POWDERED CATALYSTS
1 CHOICE OF METAL
2 CHOICE OF SUPPORT
3 MASS TRANSPORT AND REACTOR DESIGN
4 CATALYST DESIGN
5 CATALYST SEPARATION, FILTRATION
6 PROCESS ECONOMICS
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VULCAN Catalytic Reaction GuideChemistry Reactions
1. Hydrogenation 1-55
1.1 C-C Multiple Bonds 1-7
1.2 Aromatic Ring Compounds 8-14
1.3 Carbonyl Compounds 15-25
1.4 Nitro and Nitroso Compounds 28-351.5 Halonitroaromatics 36
1.6 Reductive Alkylation's 37 & 38
1.7 Imines 39-41
1.8 Nitriles 42-47
1.9 Oximes 48-49
1.10 Hydrogenolysis 50-54
1.11 Other 55
2. Dehydrogenation 56-60
3. Hydrofo rmylation 61& 62
4. Carbonylation 63-68
5. Decarbonylation 69
6. Hydrosilylation 70 & 71
7. Cross Coupling 72-96
Catalytic Reaction Guide: (106) Heterogeneous Reaction Mechanisms
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0 HETEROGENEOUS POWDERED CATALYSTS
Supported precious metal catalysts are used for a variety of reactionsincluding hydrogenation, dehydrogenation, hydrogenolysis, oxidation,disproportionation and isomerization. Many important organictransformations are completed via catalytic hydrogenation. A large numberof these reactions are carried out in the liquid phase, using batch typeslurry processes and a supported heterogeneous platinum group metal
catalyst. Platinum group metal catalysts will reduce most organicfunctional groups.
The selection of a catalyst or catalyst system for a new catalytic processrequires many important technical and economic considerations. Theprocess of selecting a precious metal catalyst can be broken down intocomponents. Key catalyst properties are high activity, high selectivity, highrecycle capability and filterability. Important process components include
choice of catalytic metal, choice of support, reactor design, heat and masstransport, catalyst design, catalyst separation, and spent catalyst recoveryand refining.
1 CHOICE OF METAL
Catalyst performance is determined mainly by the precious metalcomponent. A metal is chosen based both on its ability to complete thedesired reaction and its inability to complete an unwanted reaction.
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2 CHOICE OF SUPPORT
In general, a catalyst support should allow for a high degree of metaldispersion. The choice of support is largely determined by the nature ofthe reaction system. A support should be stable under reaction andregeneration conditions, and not adversely interact with solvent, reactantsor reaction products. Common powdered supports include activatedcarbon, alumina, silica, silica-alumina, carbon black, TiO2, ZrO2, CaCO3,and BaSO4. The majority of precious metal catalysts are supported on
either carbon or alumina. Information on common powdered supports issummarized on Page 5.
Figure 1. The Effect of Catalyst Support on Platinum Dispersion
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Support porosity affects metal dispersion and distribution, metal sintering
resistance, and intraparticle diffusion of reactants, products and poisons.Smaller support particle size increases catalytic activity but decreasesfilterability. A support should have desirable mechanical properties,attrition resistance and hardness. An attrition resistant support allows formultiple catalyst recycling and rapid filtration. Support impurities maydeactivate the metal and enhance catalyst selectivity.
The concentration of precious metal deposited on a support is typically
between 1 and 10 weight percent. Practical metal concentration limits arebetween 0.1 and 20 weight percent for activated carbon, and between 0.1and 5 weight percent for alumina. Relative catalyst activity will generallyincrease with decreasing metal concentration at constant metal loading.
3 MASS TRANSPORT AND REACTOR DESIGN
Liquid phase hydrogenations employing heterogeneous catalysts aremultiple phase (gas-liquid-solid) systems containing concentration andtemperature gradients. In order to obtain a true measure of catalyticperformance, heat transfer resistances and mass transfer resistancesneed to be understood and minimized. Mass transfer effects can alterreaction times, reaction selectivity, and product yields. The intrinsic rate ofa chemical reaction can be totally obscured when a reaction is masstransport limited. For reaction to take place in a multi-phase system,the following steps must occur: 1) transport of the gaseous reactant into
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Figure 2. Concentration Gradients in Gas/Liquid/Solid Catalytic system
of the dissolved gaseous reactant through the bulk liquid to the surface ofa catalyst particle 3) transport of the dissolved substrate through the liquid
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A reaction controlled by pore diffusion-chemical reaction, i.e. the rate of
reactant diffusion and chemical reaction within the catalyst particle, will beinfluenced mainly by temperature, reactant concentration, percent metalon the support, number and location of active catalytic sites, catalystparticle size distribution and pore structure. To evaluate and rank catalystsin order of intrinsic catalytic activity, it is necessary to operate underconditions where mass transfer is not rate limiting. A reactor used forliquid phase hydrogenations should provide for good gas-liquid and liquid-solid mass transport, heat transport, and uniformly suspend the solid
catalyst.
4 CATALYST DESIGN
The size of the deposited precious metal particulates and their location onthe support material affect the properties and performance of aheterogeneous catalyst. Increased metal dispersion and decreased metalparticle size generally result in increased catalyst activity. Metal location
and metal dispersion can be controlled during catalyst manufacture. Metalparticulates can be deposited preferentially at the exterior surface of thesupport to give what is termed an eggshell or surface-loaded catalyst.Catalysts with metal particulates evenly dispersed throughout the supportstructure are referred to as having a standard or uniform metaldistribution (Figure 3).
Figure 3. Schematic of Metal Location
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particulates can be deposited preferentially at the exterior surface of thesupport to give what is termed an eggshell or surface-loaded catalyst.Catalysts with metal particulates evenly dispersed throughout the supportstructure are referred to as having a standard or uniform metaldistribution (Figure 3).
Catalysts are designed with different metal locations for reactions whichtake place under different conditions of pressure and temperature.
Hydrogenation reactions are generally first order with respect to hydrogen.As such, standard catalysts with increased metal dispersions typicallyexhibit greater relative activity at high hydrogen pressures. Eggshellcatalysts exhibit higher relative activity at low hydrogen pressures.Hydrogenation of large molecules is generally carried out using eggshellcatalysts. Variation of metal location can also be used to alter catalystselectivity.
Location of catalytic metal deep into the pore structure of the support maylead to significant reactant pore diffusion limitations. Such catalysts,however, are generally more poison resistant because catalyst poisonsare typically of high molecular weight, and unlike smaller reactantmolecules, are unable to penetrate into the catalyst pore structure todeactivate the catalytic metal.
Deposited metal may be either in a reduced or unreduced form.
Unreduced catalysts are readily reduced under the conditions of thecatalytic hydrogenation itself, and are often more active than reduced
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5 CATALYST SEPARATION, FILTRATION
A good powdered catalyst should be easy to separate from the reactionmixture and final product. Catalyst filtration time should be minimized toensure maximum product throughput and production rates. Cycle timeadvantages gained from a high activity catalyst can be lost if catalyst
filtration becomes an extended and time consuming step.
A catalyst should exhibit high attrition resistance to reduce catalyst lossesresulting from generation and loss of catalyst fines. The generation offines will also decrease the rate of filtration. There is often a trade-offbetween catalyst performance and the rate of catalyst separation. Catalystfiltration rate and attrition resistance are largely functions of particle size,particle shape, pore volume, pore size distribution, surface area and raw
material source.
6 PROCESS ECONOMICS
It is important to consider the economic viability of a catalyst and catalyticprocess early in the selection process. The economics of using asupported precious metal catalyst depend critically on catalyst turnover
number, i.e. the amount of product produced per amount of catalyst used,and on catalytic activity or turnovers per unit time. For supported catalysts
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Typical catalyst costs include catalyst fabrication, spent catalyst refining or
disposal and precious metal charges. In the case of a catalyst returned forrefining and reclamation of the precious metal, the total metal chargesshould include only metal irrecoverably lost during the catalytic process,the refining process, and due to handling. If the maximum allowablecatalyst cost per unit weight of product is known, one can back calculateto determine required reaction selectivity and/or the number of catalystrecycles necessary to make a process economically feasible.
Most of the commonly used catalyst supports, particularly carbon andalumina, are available in a wide range of particle sizes and surface areas.
6.1 Activated Carbon
Activated carbon powder is used principally as a support forcatalysts in liquid phase reactions. As carbon is derived fromnaturally occurring materials, there are many variations, each type
having its own particular physical and chemical properties.The surface areas of different carbons can range from 500 m2g-1toover 1500 m
2g
-1.
Trace impurities that may be present in certain reaction systemscan occasionally poison catalysts. The high absorptive power ofcarbons used as catalyst supports can enable such impurities to beremoved, leading to longer catalyst life and purer products.
6.2 Alumina
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6.3 Calcium Carbonate
Calcium carbonate is particularly suitable as a support forpalladium, especially when a selectively poisoned catalyst isrequired. The surface area of calcium carbonate is low but it findsapplication where a support of low absorption or of a basic nature isrequired, for example to prevent the hydrogenolysis of carbonoxygen bonds.
6.4 Barium Sulfate
Barium sulfate is another low surface area catalyst support. Thissupport is a dense material and requires powerful agitation of thereaction system to assure uniform dispersal of the catalyst.
6.5 Other Powdered Supports
Silica is sometimes used when a support of low absorptive capacitywith a neutral, rather than basic or amphoteric character isrequired. Silica-alumina can be used when an acidic support isneeded.
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VULCAN Catalytic Reaction GuideChemistry Reactions
1. Hydrogenation 1-55
1.1 C-C Multiple Bonds 1-7
1.2 Aromatic Ring Compounds 8-14
1.3 Carbonyl Compounds 15-25
1.4 Nitro and Nitroso Compounds 28-35
1.5 Halonitroaromatics 36
1.6 Reductive Alkylation's 37 & 38
1.7 Imines 39-41
1.8 Nitriles 42-47
1.9 Oximes 48-49
1.10 Hydrogenolysis 50-541.11 Other 55
2. Dehydrogenation 56-60
3. Hydroformylation 61& 62
4. Carbonylation 63-68
5. Decarbonylation 69
6. Hydrosilylation 70 & 71
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Reactant Product Metal Support Reaction
Temp.
Reaction
Pressure
Solvents COMMENTS
(deg. C) (BAR)
Pd > Pt > Rh
Rh = Ru = Ir
C > Al2O3 =
BaSO4 BaSO4 =
CaCO3
5-100 3-10 None or low
polarity solvent
Rh, Pt or Ru used for
stereoselective application. Pd
may cause isomerization
Pd C > Al203 20-100 1-10 None or low
polarity solvent
Pd very active under mild
conditions.
Pd CaCO3 > C
C > BaSO4
5-50 1-3 Low Polarity
Solvent
Doped Catalyst (Lindlar) under
mild conditions
Pt > Rh > Pd
Pd = Ru
C > AlO3 5-100 1-10 Neutral or acidic forCl, Br Neutral or
basic for others
X = OR, OCOR, Cl, Br, NHR, No
base with halogens; no acid with
others
Pd > Ru >Pt Al2O3 > CC > CaCO3
5-100 1-3 None or a Polarsolvent
Pd most common catalyst.
Ir-40; Rh-93,
100; Ru-100
None 20-80 1-5 Various Least hindered double bond
reduced. Asymmetric
hydrogenation with chiral ligands
Pt > Pd > Rh C > Al2O3 50-150 3-10 None or low
polarity solvent
Pd may give disproportionation
1.1 C-C Multiple Bonds
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Reactant Product Metal Support Reaction
Temp.
Reaction
Pressure
Solvents COMMENTS
(deg. C) (BAR)
Rh> Pt Pt =
Ru > Pd
C > Al2O3 50-150 3-50 No solvent Rh active under mild conditions.
Pd >> Rh Al203 > C 100-150 >
150
1-50 None or low
polarity solvent
Basic promoters enhance activity /
selectivity.
Rh > Pd >
Ru
C > Al2O3 5-150 1-50 None or low
polarity solvent
Rh preferred - no selectivity
problems.
Pt >> Ir C >> Al2O3 5-150 1-50 Acidic solvent Acetic acid or alcohol/HCl
preferred.
Rh > Ru C > Al2O3 100-150 3-50 Acetic acid Pd most common catalyst.
Rh > Ru > Pt C > Al2O3 50-150 3-10 for Rh
> 50 for Ru
Low polarity
solvent
X = OH, OR, OCOR, NH2, NHR,
Rh preferred - no hydrogenolysis.
Product Reactant
Pt = Rh C >> Al2O3 30-150 3-50 None or alcohol Acetic acid may enhance activity.
1.2 Aromatic Ring Compounds
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Product Reactant Metal Support Reaction
Temp.
Reaction
Pressure
Solvents COMMENTS
(deg. C) (BAR)
Ru > Pt C > Al2O3 5-100 1-50 Low polarity
solvent
Fe2+ or Sn2+ salts promote Pt.
Water promotes Ru .
Pt C > CaCO3 5-100 1-20 Non-polar or low
polarity solvent
Modifiers required, e.g. Base, Fe2+
or Zn2+ salts.
Pd C >> Al2O3 5-100 1-10 Neutral solvent Acid causes loss of OH
Ru > Rh > Pt C >> Al2O3 50-150 1-50 Polar solvent (e.g.
water)
Ru requires high pressure.
Rh -40, 92, 93,
100 Ru-42,
100
None 25-110 1-200 Various Asymmetric Hydrogenation possible
with chiral ligands. Reduction of the
ketone also possible via
hydrosilation.
Pt C >> Al2O3 5-150 1-10 Low polarity
solvent
Modifiers required, e.g. Base, Fe2+
or Zn2+ salts.
Pd C >> Al2O3 5-50 1-10 Low polarity
solvent
Acid promotes hydrogenolysis of OH
Rh >> Ru C >> Al2O3 5-100 1-50 Low polarity or
neutral solvent
Ru requires high temperaturesand
pressures.
Pd C > Al2O3 5-100 1-10 Acidic solvent Promoted by strong acids.
Rh/Mo or
Rh/Re
Al2O3 150-200 80-100 Ethers Works bes t with 2o or 3o amides.
Poor for 1o amides.
Ru C > Al2O3 200-280 200-300 None or an
alcoholic solvent
Promoted by Sn.
1.3 Carbonyl Compoun ds
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Product Reactant Metal Support Reaction
Temp.
Reaction
Pressure
Solvents COMMENTS
(deg. C) (BAR)
Pd = Pt > Rh C 50-100 3-50 Low polarity
solvent
Bases often inhibit reaction. Prduct
amine may poison catalyst.
Reactant Product
Pd C >> Al2O3 5-100 1-10 Low polarity
solvent
Acids normally prevent dimer
formation.
Pd = Pt C > Al2O3 5-50 1-5 Various Neutral conditions
Pt > Pd = Ir CaCO3 > BaSO4
BaSO4 > Al2O3
5-100 1-5 Various Use N- or S- compounds as
moderators
Pt C 50-150 Pt > Ru C >> Al2O3 50-100 1-10 Polar or low
polarity solvent
In presence of base.
Pd >> Pt C 5-100 1-10 Low polarity
solvent
Acetic acid/mineral acid solvent
preferred
Pd = Pt C > Al2O3 5-50 1-10 Various Neutral or mildly acidic conditions
preferred
1.4 Nitro & Nitroso
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Reactant Product Metal Support Reaction
Temp.
Reaction
Pressure
Solvents COMMENTS
(deg. C) (BAR)Pt >> Rh = Pd C 5-100 1-10 Low polarity
solvent
X = halogen F >> Cl > Br > I.
Stability to hydrogenolysis
1.5 Halonitroaromatics
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Metal Support Reaction
Temp.
Reaction
Pressure
Solvents COMMENTS
Reactant Product (deg. C) (BAR)
Pd = Pt C >> Al2O3 50-150 3-50 Low polarity
solvent
Schiff base formulation catalysed
by acid.
Pd = Pt C >> Al203 50-150 1-50 None or low
polarity solvent
Often add ketone and more
catalyst after nitro reduction
1.6 Reductive Alkylations
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Reactant Product Metal Support Reaction
Temp.
Reaction
Pressure
Solvents COMMENTS
Pt C >> Al2O3 50-150 3-50 Low polarity
solvent
Acidic conditions favored.
Product Reactant
Ir-93, Rh-93,
100, Ru-100
None 25-170 1-200 DMF, Ethanol Asymmetric hydrogenation possible
with chiral ligands.
Pt C 50-100 3-50 Various Acetic acid or ethanol best.
1.7 Imines
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Product Reactant Metal Support Reaction
Temp.
Reaction
Pressure
Solvents COMMENTS
(deg. C) (BAR)
Pd = Rh > Pt C > > Al2O3 50-100 1-10 Acidic solvent or
additionof excess
ammonia.
Best Solvent is alcohol plus 1-2
equivalents of HCl or H2SO4
Rh C > > Al2O3 5-100 '1-10 Neutral solvent Rh gives good selectivity.
Pd > > Pt C >> Al2O3 5-100 1-10 Neutral solvent Pd gives best selectivity.
Pd C > Al2O3 5-100 1-10 Alcohol/acid or acetic
acid
Best solvents - acetic acid or alcohol
+ HCl or H2SO4
Pt > Pd C >> Al2O3 5-100 1-10 Low polarity solvent Use Neutral low polar solvents
Pd C 5-100 1-10 Alcohol with water &
acid
Imine intermediate hydrolyzed by
water.
1.8 Nitriles
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Product Reactant Metal Support Reaction
Temp.
Reaction
Pressure
Solvents COMMENTS
(deg. C) (BAR)
Rh >> Pd C > > Al2O3 5-100 1-10 Various Alcohol + Acid or ammonia to
minimize coupling reactions
Pd > > Rh C >> Al2O3 5-100 1-10 Acidic solvent Mineral acid/acetic acid or mineral
acid/alcohol
1.9 Oximes
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Product Reactant Metal Support Reaction
Temp.
Reaction
Pressure
Solvents COMMENTS
(deg. C) (BAR)
Pd C > > Al2O3 5-100 1-10 Low polarity solvent X = Cl, Br or I. Basic conditions
favored.
Pd C >BaSO4 5-50 1-3 Nonpolar solvent Reflux. Use N- or S- compounds as
modifiers + halogen aceptors.
Ru C > Al2O3 200-280 200-300 None or an alcoholic
solvent
Promoted by Sn.
Reactant Product
Pd > PtPt = Ru > Rh
C > Al2O3Al2O3 = CaCO3
50-150 3-50 Basic solvent for Cl &Br; acidic for others
X = OR, OCOR, Cl, Br, NHR. Withhalogens use alcoholic KOH or
NaOH, with others use alcoholic HCl
or acetic acid.
Pd C >> Al2O3 50-150 1-10 Acidic or neutral
solvent
X = OR, OCOR, Cl, Br, NHR. THF
Best for C-O cleavage. Aliphatic
carbonyls best for C-N cleavage.
1.10 Hydrogenolysis
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Reactant Product Metal Support Reaction
Temp.
Reaction
Pressure
Solvents COMMENTS
(deg. C) (BAR)
Pd C >> Al2O3 50-100 3-50 Acidic solvent Organic base may promote
selectivity.
1.11 Other
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Reactant Product Metal Support Reaction
Temp.
Reaction
Pressure
Solvents COMMENTS
(deg. C) (BAR)
Pd > Pt C >200 > 1 = 1 Various high
boiling point
solvents
Remove liberated H2 by N2 purge or
H2 acceptor in liquid phase.
Pd > Pt C > Al2O3 50-300 < 1 No solvent Pd is the only active catalyst.
Pd-62, 111 None 40-80 1-5 Methanol/water E = O, NH. Perform in presence of
reoxidant, e.g.Cu(Oac)2/O2.
Pd C 180-250 > 1 = 1 High Boiling Use dinitrotoluene as H2 acceptor.
Pd C > Al2O3 180-250 < 1 High Boiling
2. Dehydrogenation
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Reactant Product Metal Support Reaction
Temp.
Reaction
Pressure
Solvents COMMENTS
(deg. C) (BAR)
Rh-42, 43, 50,112
None 50-150 10-50 Aldehydes ortoluene
Higher normal to iso-aldehyde ratiosobtainable with Rh than with Co.
PPh3:Rh > 50:1 = 50:1
Pd-100, 111 None 50-150 10-50 Various. Base
promoted
X = Br, I R = aryl, benzyl, vinyl
Base promoted
3. Hydroformylation
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Reactant Product Metal Support Reaction
Temp.
Reaction
Pressure
Solvents COMMENTS
(deg. C) (BAR)
Pd-100, 101; Pt-100;
Rh-40, 112
None 50-150 10-50 Alcohol Use SnCl2 promoter for Pt and Pd.
Pt active for terminal alkenes only.
Pd-92, 100, 111 None 50-150 1-20 Various. Base
promoted
E = O, NH X = Br, I R = aryl,
benzyl, vinyl Base promoted
Pd-100, Rh-112,
RhI3
None 100-150 1-50 Carboxylic acids
(Rh) or ketones
(pd)
Iodide promotes Rh for !o alcohols.
Acidss promote Pd for 2o alcohols.
Product Reactant
Pd-100, 101, 111 None 25-100 1-10 Various Organic base such as Et3N, Bu3Nor inorganic bases such as
K2CO3. Ligand such as PPh3 also
required if Pd-111 is used.
Pd-100, 101 None 25-100 1-10 DMF Organic base such as Et3N, Bu3N
or inorganic bases such as
Pd-100, 111 None 50-150 1-20 Alcohol R = aryl Cu or Co promoted
4. Carbonylation
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Metal Support Reaction
Temp.
Reaction
Pressure
Solvents COMMENTS
(deg. C) (BAR)
Product Reactant
Rh-100 None 50-150 ca. 1 Various Also possible to decarbonylatesome acyl alcohols.
5. Decarbonylation
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Product Reactant Metal Support Reaction
Temp.
Reaction
Pressure
Solvents COMMENTS
(deg. C) (BAR)
Pt-92, 96, 112,
114
H2[PtCl6]
None 25-75 Ambient None,
hydrocarbons
Rh-93, 100 None 25 Ambient MeCN Z isomer obtained with EtOH or
propan-2-ol. PPh3 also requiredas
li and when Rh-93 used.
6. Hydrosilylation
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Metal Support Reaction
Temp.
Reaction
Pressure
Solvents COMMENTS
(deg. C) (BAR)
Product Reactant
Pd-62, 92, 100, 101,
111
None -10-80 ca. 1 Various M = Li, Mg, Zn, Zr, B, Al, Sn, Si,
Ge, Hg, Ti, Cu, Ni.
Pd-92, 100, 111 None 50-150 1-3 Amine or toluene X = Br, I, Otf. Base required as HX
Scavenger.
Pd-92, 111 None 25-100 - Various Organic and inorganic bases can
be used. Various ligands can be
Pd-62, 92,101, 106,
111
None 25-100 - Various Phosphineligand required where
Pd-62, 92, 111 are used. Base
required.
7.1 Heck
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Metal Support Reaction
Temp.
Reaction
Pressure
Solvents COMMENTS
(deg. C) (BAR)
Product Reactant
Pd-92, 101, 111 None 25-100 - Various Base required, generally inorganic.
Various ligands can be used in
conjunction with Pd precursor e.g.
PPh3, P(o-to)3, t-Bu3P.
7.2 Suzuki
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Metal Support Reaction
Temp.
Reaction
Pressure
Solvents COMMENTS
(deg. C) (BAR)
Product Reactant
Pd-92,111, 106 None 80-100 - THF, toluene Base required, t-BuONa orCs2CO3. Ligand such as P(o-to)3,
t-Bu3P, BINAP required when Pd-
92 or Pd-111 used.
Pd-92, 111 None 80-100 - toluene Specialist ligand required. Base
such as K3PO4, NaOH required
when R'OH used as substrate.
7.3 Buckw ald-Hartwig
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Metal Support Reaction
Temp.
Reaction
Pressure
Solvents COMMENTS
(deg. C) (BAR)
Reactant Product
Pd-100, 101 None 25-reflux - DMF, THF Addition of CuI as a co-catalyst
activates acetylene by formation of
copper acetylide. Organic base e.g.,NR3 usually used.
Pd-111 None 25-100 - DMF Base required K2CO3 or Na2CO3,
Bu4NClalso required. Reaction
performed under phase transfer
conditions, hence the need for
Pd-100 None 65 - THF Use Cul as additive.
Pd-62, 100, 111 None 25-reflux - NHEt2, NEt3 The addition of Cul as co-catalyst
activates the acetylene by formation of
a copper acetylide. Poor results are
obtained without Cul. The use of
amines is critical.
7.5 Sonogashira
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Metal Support Reaction
Temp.
Reaction
Pressure
Solvents COMMENTS
(deg. C) (BAR)
Reactant Product
Pd-62, 111 None 40-80 1-5 Methanol/water E = O, NH, Perform in presence of
reoxidant, e.g., Cu(Oac)2/O2
Pd-92, 111 None 25-100 - Toluene, THF,
dioxane
Base required NaOtBu, K3PO4
enerall used S ecialist li and
Ru-120 + prop-2-yn-1-
ol, NaPF6 + P(Cy)3
None 25-80 Ambient Toluene,
dichloromethane
Pd-62 None 65 - THF Use LiCl as additive. Use of a mild
reoxidant such as benzoquinone is
required.
Pd-62, PdCl2 None 65 - THF Use NaCO3 or NaH as additives.
Product Reactant
PdCl2 None 80 - Acetonitrile
Pd-111, PdCl2 None 25-65 - THF Lithiation of the alcohol using n-
BuLi in THFis requried as the initial
step. Palladium precursor used inconjunction with PPh3.
Pd 92 101 111 None 25 65 THF Ligand required when using Pd 92
7.6 Other
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Metal Support Reaction
Temp.
Reaction
Pressure
Solvents COMMENTS
(deg. C) (BAR)
Product Reactant
Pd-111; Rh-110, 115 None 20-50 ca. 1 Various Asymetric cyclopropanation
possible with chiral ligands.
8. Cyclopropanation
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Metal Support Reaction
Temp.
Reaction
Pressure
Solvents COMMENTS
(deg. C) (BAR)
Product Reactant
Ru-100, 130 None 25-110 Ambient MeCN, PhCl,
toluenedichloromethane
N-methyl-morpholine-N-oxide or
oxygen used as co-oxidant.TEMPO also required as ligand
when Ru-100 used.
Pt, Pd, Ru C, Al2O3 30-70 1-3 Toluene,
hydrocarbons
Use air as oxidant.
Pt, Pd, Ru C, Al2O3 '30-70 1-3 Toluene,
hydrocarbons
Use air as oxidant.
Ru-100, 130 None 25-110 Ambient MeCN, PhCl,
toluene
dichloromethane
N-Methyl-morpholine-N-oxide
oroxygen used as co-catalyst.
TEMPO also required as ligand
when Ru-100 used.
Pt > Pd C 40-60 1-5 Aqueous Basic pH (8-10) essential.
9.1 Alcohols to Carbonyls
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Metal Support Reaction
Temp.
Reaction
Pressure
Solvents COMMENTS
(deg. C) (BAR)
Product Reactant
OsO4/K2[OsO2(OH)4]
None 0-50 ca. 1 t-butanol, water,THF
Oxidants such as N-methylmorphine N-oxide or
K3Fe(CN)6 preferred. Asymetric
hydroxylation possible with chiral
l i ands.
9.2 Dihydroxylation of Alkenes
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Metal Support Reaction
Temp.
Reaction
Pressure
Solvents COMMENTS
(deg. C) (BAR)
Product Reactant
Pd-111 None 20-50 1-5 Acetic acid oralcohol
O2 or H2O2 used as oxidant.Cu2+ co-catalyst.
9.3 Oxygen Insertion Reactions
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Metal Support Reaction
Temp.
Reaction
Pressure
Solvents COMMENTS
(deg. C) (BAR)
Product Reactant
RuCl3, Ru-100 None 25-70 ca. 1 Various H2O2 or NaOCl oxidant.
PdCl2 None - - Water, DMF. Aq.
HCl
Use CuCl2/O2 as additives.
9.4 Other
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