Organometallic Chemistry

and
Homogeneous Catalysis

MST - ANO 1
 Role of metal ions in catalysis **

• Stabilization of reactive species (e.g. radicals)

• Activation of inert species (e.g. carbon monoxide)
• Bring together substrate and reagents (template
effect)
• Electron transfer (redox reactions)
• In general: Lewis acid

MST - ANO 2
 (Homogeneous) catalysis in industry
• Roelen OXO process: hydroformylation
– 1st generation: Roelen [HCo(CO)4]
– 2nd generation: Shell Rh – PR3 complexes (~1960)
– 3rd generation: water soluble P-ligands
• SHOP: oligomerisation of ethene (Ni – P-O)
• Acetic acid from methanol (Rh / I)
• Dimerisation of butadiene (Ni)
• Polymerisation of butadiene (Ti, Co, Ni)
• Hydrocyanation of butadiene (Ni)
• Ziegler-Natta polymerisation of propene
MST - ANO 3
 Important reactions in biology

• Photosynthesis CO2 + H2O  O2 + [CH2O]n

• Cytochrome oxidase O2  H2O
• Nitrogenase N2  2 NH3
• Superoxide dismutase 2 O2–  H2O2 + O2
• Catalase 2 H2O2  2 H2O + O2
• Methane monooxygenase CH4  CH3OH

All these enzymes use metal ions;

often more than one metal ion!
MST - ANO 4
 Fast and specific reactions
1. Catalase (Fe-containing enzyme):
H2O2  H2O + O2: 2x106 /sec
2. Superoxide dismutase (Cu-enzyme)
O2–  H2O2 + O2: 2x109 /sec
3. Fastest catalysis in industry: Polymerisation of
ethene; 104 ethene molecules per second;
1 mole PE in 0.3 sec!
200 tonnes polymer/g catalyst (Zr,Al).
Chiral catalysis with a Ru catalyst
Preparation of menthol (400000 ton/y); Japan.
MST - ANO 5
 12 principles of Green Chemistry
1. Prevent waste instead of clean up. Atom efficiency
2. Maximize the incorporation of all materials into the final product.
3. Synthetic methodologies should use and generate substances that
possess little or no toxicity.
4. Develop products for function while reducing toxicity.
5. Lower the use of auxiliary substances (e.g. solvents).
6. Energy requirements should be minimized.
7. Feedstock should be renewable rather than depleting.
8. Reduce number of synthesis steps (protection/deprotection).
9. Make use of catalysis. E factor
10. Design products for their degradation.
11. Analyze and monitor reactions to prevent pollution.
12. Minimize potential for chemical accidents.
MST - ANO 6
 E Factor
• The E factor is the actual amount of waste produced in the
process, defined as everything but the desired product.
• It takes the chemical yield into account and includes
reagents, solvents losses, all process aids and, in principle,
even fuel (although this is often difficult to quantify).
Industry segment Product E factor (kg waste/kg product)
tonnage
Oil refining 106 – 108 <0.1
Bulk chemicals 104 – 106 <1–5
Fine chemicals 102 – 104 5 - > 50
Pharmaceuticals 10 – 103 25 - > 100
R.A. Sheldon, “Catalysis: the key to waste minimization”, J. Chem. Tech.Biotechnol. (1997) 68,381-388;
R. A. Sheldon, “E factors, green chemistry and catalysis: An odyssey”, Chem. Commun. (2008) 3352-3365.
MST - ANO 7
 Atom efficiency ***
Stoichiometric oxidation
OH O
3 CH + 2 CrO3 + 6 HOAc 3 + 2 Cr(OAc)3 + 6 H2O
C
H3C CH3 H3C CH3

iPrOH (FW=60) 3 mol =180; CrO3 (FW=100) 2 mol =200; HOAc (FW=60) 6 mol =360
Total input: 740
Acetone (FW=58) 3 mol = 174 = relevant output
Atom efficiency: (174 / 740) x 100%= 23%
OH O
Catalytic oxidation CH
+ 1/2 O2
C
+ H2O
H3 C CH3 H3C CH3

iPrOH (FW=60) 1 mol =60; O2 (FW=32) ½ mol = 16. Total input: 76

Aceton (FW=58) 1 mol =58 = relevant output
Atom efficiency: (58 / 76) x 100%= 76%
MST - ANO 8
 Atom efficiency *
2 HCN + 2 NaOH 2 NaCN + 2 H2O

+ 2 HCl Cl Cl

+ 2 NaCN + 2 NaCl
Cl Cl N C C N

Atom efficiency: (108 / 261) x 100% = 41%

+ 2 HCN N C C N

Atom efficiency: 100%

MST - ANO 9
 Bulk chemicals

• Feedstock • Substrates / Reagents

– Coal
– Oil
– Syngas
– Gas – Methane
– Biomass – Ethene / propene / butenes
– CO2
– Benzene / toluene / xylene

MST - ANO 10
 Reactions of olefins

• Isomerisation
• Metathesis
• (cyclo-) oligomerisation
• Polymerisation
• Addition of H2
HY
H2 / CO
• Oxidation

MST - ANO 11
 Homogeneous Catalysis **

Lowering the energy

barrier using stable
intermediates

MST - ANO 12
 Homogeneous Catalysis **

Uniform composition
Activation of hindered substrates is possible
Fine tuning catalyst using ligands
Mechanism predictable/understandable

Cumbersome separation catalyst/product

Catalyst is sensitive
MST - ANO 13
 Fine tuning of catalyst

H2C CH2 + CO + H3C OH + Pd(OAc)2

MST - ANO 14
 Controllable selectivity

MST - ANO 15
 Homogeneous catalysis ***
and coordination chemistry…
• d-Block metals
– geometry
– oxidation state
– open sites
– 14 VE, 16 VE, or 18 VE complexes
• Ligands
–  or  bonding,  back bonding
– HSAB
– electron donating / withdrawing ligands
– steric effects
– chirality
MST - ANO 16
 Enantioselectivity *

prochiral substrate enantiomeric pair

racemic mixture

Enantiomeric Excess (EE) = % major – % minor

example: 70% R, 30% S EE = 40%

MST - ANO 17
 Homogeneous catalysis **
and organometallic chemistry…
• Reactions
– Association/dissociation
– oxidative addition
– reductive elimination
– migration
– -hydrogen elimination
• Reaction cycle
• Mechanism

MST - ANO 18
 Most important reactions

Reaction Valence Coordination Electron count

change number
Oxidative addition +2 +2 +2
(16 to 18)
reductive elimination –2 –2 –2
Ligand migration none –1 –2
Ligand addition none +1 +2
Ligand dissociation none –1 –2
Ligand substitution none same same

MST - ANO 19
 Hydrogenation of olefins

CH3 CH3
RO O
CH3
O
H3C
CH3
O O

OH H2
ivermectin

O CH3
chemoselectivity OH

Wilkinson’s catalyst

MST - ANO 20
 H2 activation: oxidative addition
• Wilkinson’s catalyst

MST - ANO 21
 Wilkinson’s Catalyst ***

MST - ANO 22
 Ligand effects in [RhX(PR3)3]

Electronic effects Steric effects

Relative rates of reaction

Electronic and steric

properties of the substrate
MST - ANO 23
 Hydroformylation

Catalyst: [HRh(CO)2(PR3)2]

MST - ANO 24
 Hydroformylation: [HRh(CO)2L2] ***

MST - ANO 25
 Production of acetic acid

CH3OH + CO X

O
CH3OH + CO CH3COH
MST - ANO 26
 Olefin metathesis

Phillips triolefin process

Pheromone house fly

Fly strips
MST - ANO 27
 Catalysts: metal carbenes

1st generation Grubbs catalyst

Fluka’s reagent of the year 1998

MST - ANO 28
 Alternative synthesis routes
CH3

CH3
O O N N
O O
C C
CH3 O O

EPON 828
Epoxy resin, used in glue, coatings 2,4-toluene diisocyanate
Used in PUR foams
Produced with chloride salts Produced from highly
and chlorinated by-products toxic phosgene

We design and develop novel catalysts for new catalytic reactions!

MST - ANO 29
 Caprolactam from biomass O
O
OH

NH3, CO, H2

+ H2O
N O
H
MST - ANO 30
 Current process for caprolactam
Feedstock: benzene, phenol, toluene
Producing: 4-5 kg (NH4)2SO4 per kg caprolactam

OH
OH O N H
N O
H2 [O] NH2OH H2SO4
+

Caprolactam

H
N O O H
Caprolactam: 7 Mt/a
N Nylon-6: 6 Mt/a
n
Estimated overall growth: 8-10% per year
Caprolactam Nylon-6

MST - ANO 31
 Biomass as renewable feedstock

Oils Lignin

(Hemi-) Cellulose Proteins

O
+
H /H2O
OH
- H2O O - HCOOH H3C
O OH O
hydroxymethyl furfural levulinic acid
MST - ANO 32
 From levulinic acid to caprolactam

Theoretical atom efficiency = 68%; only H2O as by-product

MST - ANO 33
 “Summary”
Activation of substrate and reagents at metal center
• Properties of LnM determine product

S = CO, C2H4 etc

X = H, alkyl, acyl, OMe, I etc

Activation of the substrate for Nucleophilic or Electrophilic attack

Electron donating or
withdrawing
properties of LnM
MST - ANO 34
 Summary

• Homogeneous catalysis, advantages/

disadvantages; role of metal ion
• Oxidative addition, reductive elimination,
migration/insertion
• Mechanism of hydrogenation, hydroformylation,
carbonylation of methanol
• Atom efficiency, green chemistry!

MST - ANO 35