CH 409/609, Spring 2011

Dr. Shaughnessy
Problem Set #4
Due: Friday, April 29
th
, 2011
Name:
1. Stereoerrors during propylene polymerization catalyzed by early transition metals may not be
the result of insertion of the wrong olefin face. Rather they may result from epimerization of
the Zr-alkyl species.


a. Propose a mechanism for the isomerization shown above. You can assume that the
polymer chain does not dissociate from the metal center during this process. Feel free to
simplify the metallocene structures in your mechanisms ((EBTHI)Zr), but be sure to
show the appropriate stereochemistry for the chirality center.









b. One piece of data supporting epimerization as a source of stereoerrors, is that many
metallocene systems give lower isotacticity at low propylene concentration. Explain how
this observation supports epimerization rather than insertion errors as the mechanism for
stereoerror formation.
Zr
L
P
H
CH
3
Zr
L
P
CH
3
H
2. Provide a catalytic cycle for the reactions below. Provide the oxidation state and total
electron count for each intermediate species.

O
N
N
Pd
H
NCCH
3
+
BF
4
catalytic
O
CH
3
a.


O
Ts
N
SiMe
2
CH
2
Ru
Cl
Cl
Cy
3
P
PCy
3
Ts
N O
SiMe
2
H
b.

c.
Cp
2
TaH
3
D
2
D
D
D
D
D
D
You only need to show
replacement of one H with D
3. The compound Cp
2
Ti(!
2
-Me
3
SiCCSiMe
3
) (1) is a ready precursor of the titanocene
fragment. The C-C bond in the coordinated alkyne measures 1.283(6) and the C-C-Si
angles are 146 and 148. Compare these structural features those of a typical alkyne and
explain how coordination to the metal center affects the alkyne structure.