Chem 1140; Catalysis

• 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

How do you correlate rate constants to activation barriers? transition state

Arrhenius Equation kforward

k (rate constant) = A e(-E/RT) reactant

DG‡
where A = “frequency factor”, and
e(-E/RT) = activation energy
DGreleased
product
Eyring Absolute Rate Theory

k (rate constant) = [kbT/h]e(-DG*/RT) = [kbT/h]e(DS*/RT) e(-DH*/RT)

 Ziegler-Natta Catalysis of
Alkene Polymerization

A typical Ziegler-Natta catalyst is a combination

of TiCl4 and (CH3CH2)2AlCl, or TiCl3 and
(CH3CH2)3Al.
Many Ziegler-Natta catalyst combinations
include a metallocene.
 Ziegler’s Discovery
• 1953 K. Ziegler, E. Holzkamp, H. Breil & H. Martin
• Angew. Chem. 67, 426, 541 (1955); 76, 545 (1964).

Al(Et)3 + NiCl2 CH3CH2CH=CH2 + Ni + AlCl(Et)2

100 atm
110 C
+ Ni(AcAc) Same result

+ Cr(acac) White Ppt. (Not reported by Holzkamp)

+ Zr(acac) White Ppt. (Eureka! reported by Breil)

Al(Et)3 + TiCl4 CH2CH2

1 atm "linear"
20-70 C Mw = 10,000 - 2,000,000
 Natta’s Discovery
• 1954 Giulio Natta, P. Pino, P. Corradini, and F. Danusso
• J. Am. Chem. Soc. 77, 1708 (1955) Crystallographic Data on PP
• J. Polym. Sci. 16, 143 (1955) Polymerization described in French

CH3 CH3 CH3 CH3

TiCl3
CH3
Al(Et)2Cl
Isotactic
CH3
CH3 CH3 CH3
VCl4 - 78 C
CH3
Al(iBu)2Cl
CH3
O in Syndiotactic

Ziegler and Natta won Nobel Prize in 1963

Mechanism of Coordination Polymerization

Al(CH2CH3)3 + TiCl4 ClAl(CH2CH3)2

+
CH3CH2TiCl3
Mechanism of Coordination Polymerization

Al(CH2CH3)3 + TiCl4 ClAl(CH2CH3)2

+
CH3CH2TiCl3

CH3CH2TiCl3 + H2C CH2

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

Noncoordinating Anion, NCA

Alkene Hydrogenation with Wilkinson’s Catalyst

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

DIOP CHIRAPHOS DIPAMP

BPPM

R R R R
PPh2
PPh2 P P P P

R R R R

BINAP DuPHOS BPE

 Asymmetric Hydrogenation

R CO2Me R' CO2Me

Me BPE Rh or
H2
R' NHAc Me DuPHOS Rh R NHAc
90 psi, PhH
96-99% ee
Asymmetric Hydrogenation
R2 CO2H Ru(OCOR)2 (binap) R2 CO2H
H2
R3 R1 R3 R1
96-99% ee

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

H2 rate limiting H2 very

fast k2 step k'2 slow
Mechanism: Halpern, J. Science 1982, 217, 401-407.

minor major

Ph L diastereoisomers L Ph L
L Rh
Rh
O O
<5% >95%
MeO2C N N CO2Me
H H

H2 rate limiting H2 very

fast k2 step k'2 slow

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

k4 ee lower at high H2 pressure - k'2 increased k'4

lower at
low temp - equilibration
decreased. Major
Ph diast. accumulates Ph
H O O
H
MeO2C N
H N CO2Me
H
(R) > 98% (S) < 2%