H Organometallic Catalysis in Industry

H Organometallic Catalysis in Industry
Some terminology:
Catalytic cycles: a circular path meant to show productive reactions, in order, that lead from the
catalytically active species and its reaction with a substrate through to product elimination and regeneration of
the catalyst.
Turnover number: number of times a cycle is completed before the catalyst dies. Typically this is > 1000; a
stoichiometric reaction has a TON of 1.
Turnover rate or frequency: the rate at which a cycle is completed. This can be reported in many ways but
it is usually in mol product per mol catalyst per time. Eg. a good ethylene polymerization catalyst might have a
turnover rate of 5000 kg polyethylene per mol of catalyst per hour.
Resting State: this is the stable, and usually inactive, form of the catalyst when no substrate is provided or
when it has been used up. Eg. with a coordinated solvent molecule occupying the active coordination site.
Pre-catalyst: the stable compound put into the reactor; it must be transformed in situ into the active species.
Eg. Cp2ZrCl2 in Z-N polymerizations where MAO is the activator.
So why transition metals?
 wide range of bonding modes

  and  bonds
 many valence electrons
 wide choice of ligands

 ionic or neutral
 tunable properties
 choice of metal
 electronic and steric effects of ancillary ligands
 variable coordination numbers

 4 and 5 or 5 and 6 coordinate geometries accessible for same metal
 variable oxidation states

 ox. states separated by 2 units facilitate oxidative addition and reductive elimination reactions
Tolman’s rules: (really only apply to middle and late T.M.)
• Diamagnetic organometallic complexes may exist in significant concentration only if the metal’s
valence shell contains 16 or 18 electrons. A significant concentration is one that can be detected
spectroscopically or kinetically.
• Organometallic reactions, including catalytic ones, proceed by elementary steps involving only
intermediates with 16 or 18 valence electrons.
As a corollary, there is an old saying in catalysis that says:

‘If you can isolate it, then it isn’t the active catalyst’
This statement has been shown to be untrue in many catalytic systems in more recent work
Industrial Importance of Homogeneous Catalysis
Reaction and Products Ann. Production World (2015)

103 metric tons
Olefin additions
Adiponitrile (for nylon) 1,200
Olefin polymerizations (all types) 100,000+
Carbonylations
Oxo alcohols (hydroformylation) 2,000
Acetic acid/anhydride (from MeOH) 2,500
Olefin oxidation
Acetaldehyde 1,250+
Propylene oxide 7,500
Alkane and arene oxidations

Terephthalic acid and esters 5,000+
Adipic acid (for nylon) 1,200+
1. Isomerization of Alkenes  often unwanted side reaction but can be useful in some cases
 most metal hydride species will do this to some extent
2. Hydrogenation
Most important for alkenes: usually oxidative addition / reductive elimination sequences
Wilkinson’s catalyst is the original system and most famous but many are now known
 selective for C=C over C=O and CN
 does not scramble H and D
 exclusively syn H2 addition (see e.g. below)
 commercially available
Wilkinson’s catalyst:
Insertion is turnover limiting
Many cationic hydride complexes are also used: one example is [Rh(dppe)(L)2]+
Oxidative-addition is
turnover limiting
Asymmetric hydrogenation:
Chiral chelating ligands result in

preferential delivery of H2 to one
enantiotopic face of the alkene
Chiral chelating phosphines are

among the most popular
Some examples of asymmetric
hydrogenation of alkenes using
a related Ir catalyst:
Ph
Ph
O
O PPh2
N
Ligand 15.12
Asymmetric transfer hydrogenation of ketones: asymmetric Meerwein-Pondorff-Verley reduction
Reaction occurs with Lewis acids too: alumina, lanthanide and group 4 metal complexes
No oxidation state
change for the metal
3. Hydroformylation (Oxo process)
O
R
+ H2 + CO
R H
synthesis gas
• Formally addition of formaldehyde across a double bond

• Discovered by BASF by Otto Roelen using Co catalysts
• Worldwide scale: about 7 BILLION kgs per year
 HCo(CO)4 catalyst:
conditions 110-180 C / 200-300 atm
 linear/branched ratio is about 3:1

 internal alkenes isomerize to terminal so
only  or  aldehydes formed
 problem: catalyst loss due to volatility of
HCo(CO)4 and Co2(CO)8
 HRh(CO)(PPh3)2 allows lower T (100 C)
and P (6 atm)
 linear to branched ratio: > 10:1
 hydrogenation is much slower under
the conditions used and does not
compete as a side reaction.
4. Monsanto Acetic Acid Process (carbonylation of MeOH)
 acetic acid for industrial uses:

vinyl acetate, cellulose acetate,
pharmaceuticals, dyes and
pesticides.
 Monsanto process dominates the
market but older methods such
as the oxidation of ethylene via
acetaldehyde are still practiced.
 conditions: 180 C / 30-40 atm /
10-3 M catalyst
5. Alkene Oxidations: the Wacker process
• used to prepare acetaldehyde for conversion to acetic acid

• replaced dangerous hydration of acetylene in 1950’s
• now largely superceded by Monsanto process
• ultimate oxygen source is air although the reaction chemistry occurs solely at Pd
Some debate over
whether inter‐ or
intramolecular attack
occurs
Evidence for intramolecular attack from labelling studies:
Oxidative Amination: closely
related to Wacker Chemistry
6. Hydrofunctionalization of Alkenes
• Hydroamination H-NR2 (covered earlier)

• Hydrozirconation H-ZrX3 (covered earlier)
• Hydrocyanation H-CN
• Hydrosilylation H-SiX3
• Hydroboration H-B(OR)2
General mechanism is pretty much the same for all later transition metals:
R
X
X
R
M
oxid-addn
HX
red-elim
X
M
H
X X insert X
or alkene
M M M
R coord.
H
R
R
Hydrocyanation
• By far the most common catalysts are Ni0 complexes like NiL4 or chiral variants, Ni(L2*)2
• Used industrially to produce adiponitrile for nylon synthesis and one route to Naproxen
(tradename: Alleve)
Naproxen
Hydrosilylation
• Usual catalysts are Pt0 complexes like Speier’s and Karsted’s catalysts (below)
• Catalyst loadings are incredibly low (highly active catalysts): 10-5 mol% common
• Still controversy over whether it is actually colloidal Pt that is the catalyst (induction period?)
• Industrial uses: polysiloxanes for caulkings, gaskets, coatings, etc.
Speier’s catalyst: H2PtCl6
Kartsed’s catalyst: widely used Pt0 but still induction period

Asymmetric variants used in organic synthesis
‐bond metathesis alternative: no oxidative-addn / red. elim
Hydroboration
• Late transition metal catalysts (Rh, Ir, Pd, Pt, Ni) by oxid. add. / red. elim. AND early transition
metals and lanthanides by -bond metathesis
• Mostly used in organic synthesis for regio- and stereoselective alcohol formation

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H Organometallic Catalysis in Industry

 wide range of bonding modes

 wide choice of ligands

 variable coordination numbers

 variable oxidation states

As a corollary, there is an old saying in catalysis that says:

Reaction and Products Ann. Production World (2015)

Olefin polymerizations (all types) 100,000+

Alkane and arene oxidations

Chiral chelating ligands result in

Chiral chelating phosphines are

• Formally addition of formaldehyde across a double bond

 linear/branched ratio is about 3:1

 acetic acid for industrial uses:

• used to prepare acetaldehyde for conversion to acetic acid

• Hydroamination H-NR2 (covered earlier)

Speier’s catalyst: H2PtCl6

Kartsed’s catalyst: widely used Pt0 but still induction period

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