Beruflich Dokumente
Kultur Dokumente
• General Principles
• Ziegler-Natta Olefin Polymerization
• Mechanism of Hydrogenation with Wilkinson’s
Catalyst
• Asymmetric Hydrogenation
Catalysis
• Catalysts increase reaction rate without
themselves being changed
• Can accelerate a reaction in both directions
• Do not affect the state of equilibrium of reaction
– simply allow equilibrium to be reached faster
Activation energy
• Molecules must be
activated before they
can undergo a reaction
– Reactants must absorb
enough energy from
surroundings to
destabilize chemical
bonds (energy of
activation)
• Transition state
– Intermediate stage in
reaction where the
reactant molecule is
strained or distorted but
the reaction has not yet
occurred
Activation energy
• A catalyst lowers the
energy of activation by:
– Forcing molecules into
conformations that favor
the reaction
• I.e. the catalyst may re-
orientate molecules
• Change in free energy is
identical to uncatalyzed
reaction: the catalyst does
not change the
thermodynamic
equilibrium!
Activation energy
• Sometimes catalysts
cause one large
energy barrier to be
replaced by two
smaller ones
– Reaction passes
through intermediate
stage
Energy and Time
CH3CH2TiCl3
H2C CH2
Mechanism of Coordination Polymerization
TiCl3
CH3CH2CH2CH2
CH3CH2TiCl3
H2C CH2
Mechanism of Coordination Polymerization
TiCl3
CH3CH2CH2CH2
H2C CH2
TiCl3
CH3CH2CH2CH2
Mechanism of Coordination Polymerization
CH3CH2CH2CH2CH2CH2
TiCl3
H2C CH2
TiCl3
CH3CH2CH2CH2
Mechanism of Coordination Polymerization
CH3CH2CH2CH2CH2CH2
TiCl3
H2C CH2
etc.
General Composition of Catalyst System
Group I – Transition Metals Additives
III Metals
AlEt3 TiCl4 H2
Et2AlCl a,g, d TiCl3 O2, H2O
EtAlCl2 MgCl2 Support R C CH
i-Bu3Al VCl3, VoCL3, R-OH
V(AcAc)3 Phenols
Et2Mg Titanocene dichloride R3N, R2O, R3P
Et2Zn Ti(OiBu)4 Aryl esters
Et4Pb (Mo, Cr, Zr, W, Mn, HMPA, DMF
Ni)
Kaminsky Catalyst System
W. Kaminsky et.al. Angew. Chem. Eng. Ed. 19, 390,
(1980); Angew. Chem. 97, 507 (1985)
CH3
X +
Me * Al O *
n
X Linear HD PE
Al:Zr = 1000
Activity = 107 g/mol Zr
Me = Ti, Zr, Hf
CH3
Atactic polypropylene
Activity = 106 g/mol Zr
Methylaluminoxane: the Key Cocatalyst
toluene CH3
Al(CH3)3 + H2O * Al O *
0C n
n = 10-20
CH3
MAO
Al
O O CH3
Al O Al
AlAl CH3
O O O
Al Al Proposed structure
Nature of active catalyst
X CH3
Cp2Me + * Al O *
n Transition metal
X
alkylation
MAO
CH3 CH3 X
Cp2Me + Al O Al
X m O
CH3 X X Ionization to
CH3 form active sites
Al O Al O
Cp2Me + m
H2
cat. RhCl(PPh3)3
CO2Me CO2Me
CO2Me H2 96:4
cat. PtO2 49:26
Mechanism PPh3
H Rh H
oxidative
addition Cl R' coordination
H H PPh3
R
PPh3
-PPh3 Cl
[RhCl(PPh3)2] RhCl(PPh3)3
+PPh3 R' H Rh H
R PPh3
reductive
elimination PPh3 migratory
Cl Rh H insertion
R
R' PPh3
H H
H
R
R'
Enantiomerically Enriched Phosphines
PPh2
H Ph *
PH *
O PPh2 PPh2 PPh2
* N *
PPh2 *
O * * P*
H PPh2 Ph PhOMe O O
R R R R
PPh2
PPh2 P P P P
R R R R
CO2H
MeO R1 R2 R3 ee
97% ee (Naproxen) Me Me H 91
H Me 87
R3SiO
H H
H Me Ph 85
CO2H
Ph H H 92
NH H HOCH2 Me 93
O
H CH3 COOCH2CMe 95
74% de (Thienamycin)
Mechanism: Halpern, J. Science 1982, 217, 401-407.
Ph
P S O
Rh equilibrium
P S MeO2C N must be
H fast for high ee
k' k'
minor k'-1 major
k'-1
Ph L diastereoisomers L Ph L
L Rh
Rh
O O
<5% >95%
MeO2C N N CO2Me
H H
minor major
Ph L diastereoisomers L Ph L
L Rh
Rh
O O
<5% >95%
MeO2C N N CO2Me
H H
H H
Ph
Ph
L L k2 > k'2 >103 L L
Rh Rh
H H
MeO2C HN O
O NH CO2Me
Mechanism: Halpern, J. Science 1982, 217, 401-407.
Mechanism: Halpern, J. Science 1982, 217, 401-407.
H H
Ph
L Ph
L L L
Rh Rh
H H
MeO2C HN O
O NH CO2Me
k3 k'3
S
L L S
Ph Rh L L
H Ph
H H Rh
MeO2C NH O H
O HN CO2Me
Mechanism: Halpern, J. Science 1982, 217, 401-407.
S
L L S
Ph Rh L L
H Ph
H H Rh
MeO2C NH O H
O HN CO2Me