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Organozinc Reagent
Iodomethylzinc iodide
reacts with alkenes to form cyclopropanes
reaction with alkenes is called the
Simmons-Smith reaction
CH2I2 + Zn ICH2ZnI
Cu
formed by reaction of diiodomethane with
zinc that has been coated with copper
(called zinc-copper couple)
diethyl ether
Example
H2C C
CH2CH3
CH3
CH2I2, Zn/Cu
CH2CH3
CH3
(79%)
Stereospecific syn-addition
diethyl ether
CH2I2, Zn/Cu
C C
CH3CH2 CH2CH3
H H
CH3CH2 CH2CH3
H H
Stereospecific syn-addition
diethyl ether
CH2I2, Zn/Cu
C C
CH3CH2
CH2CH3
H
H
CH3CH2
CH2CH3
H
H
Ziegler-Natta Catalysis of
Alkene Polymerization
The catalysts used in coordination
polymerization are transition-metal organic
compounds.
Ziegler-Natta Catalysts
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.
Mechanism of Coordination Polymerization
Al(CH2CH3)3 + TiCl4 ClAl(CH2CH3)2
+
CH3CH2TiCl3
Mechanism of Coordination Polymerization
H2C CH2
Al(CH2CH3)3 + TiCl4 ClAl(CH2CH3)2
+
CH3CH2TiCl3
CH3CH2TiCl3 +
CH3CH2TiCl3
H2C CH2
Mechanism of Coordination Polymerization
CH3CH2TiCl3
H2C CH2
Mechanism of Coordination Polymerization
CH3CH2TiCl3
H2C CH2
TiCl3
CH3CH2CH2CH2
Mechanism of Coordination Polymerization
H2C CH2
TiCl3
CH3CH2CH2CH2
TiCl3
CH3CH2CH2CH2
H2C CH2
Mechanism of Coordination Polymerization
TiCl3
CH3CH2CH2CH2
H2C CH2
TiCl3
CH3CH2CH2CH2CH2CH2
Mechanism of Coordination Polymerization
TiCl3
CH3CH2CH2CH2CH2CH2
H2C CH2
etc.

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