J . Am. Chem. SOC.1990, 112,4954-4956
4954
Scheme I
Table I. Cyclopolymerization of 1,5-Hexadiene in Tolueneo m e t a h e n e (umol) T, OC time, min conversn, % trans! % 60 11.1 80 21 (4.8) Cp,ZrCl2 60 25.0 79 22 (4.8) Cp2ZrMe2 270 56.0 84 0 (6.7) Cp2ZrMe2 420 0.6 91 -78 CpzZrMe2 (14.3) 180 46.0 30 20 (3.4) Cp*,ZrCI2 330 65.0 14 (9.2) -25 Cp*,ZrCI2 dConditions: 5 mL of 1,5-hexadiene, AI/Zr = 2500. bFrom C4,5 cis/trans ratio. ~
A%%+
CUCI,
~~
H-c3c-R-c3+ 111-4s
02,
65 'C
___)
pyridine, TMEDA odichlorobenzene
/
200
The trans selectivity in the presence of the Cp2ZrX2catalysts can be rationalized by a preference of the growing polymer chain to adopt an equatorial position in a pseudo-chair transition state in the cyclization. However, inspection of molecular models suggests that a chair-type transition state is not readily accommodated in the presence of the more sterically hindered Cp* ligands. A twist-boat conformation could be accommodated, but placement of the polymer chain in the equatorial position in this case would lead to a cis ring. In conclusion, homogeneous Ziegler-Natta catalysts are efficient for the cyclopolymerization of nonconjugated diolefins. High-molecular-weight polymers can be readily obtained from monomers which form strained olefins upon j3-hydrogen elimination, and polymers with a range of microstructures can be obtained by choice of the appropriate catalyst precursor.
1 b-4b
- soooc
1C4c
Acknowledgment. We gratefully acknowledge Himont Italia for salary support for L.R. and partial support from the NSFMRL Program through the Center for Materials Research at Stanford. Differential scanning calorimetry was made possible by a gift from A T L T Corporation. R.M.W. is the recipient of a Du Pont Young Faculty Award, for which he is grateful. We thank J. Doug Meinhart of JEOL for assistance with the "C N M R spectra.
(X
=
F, N, Si)
