Steven A. Krouse, R. Schrock
Nov 8, 1988
Citations
0
Influential Citations
7
Citations
Journal
Journal of Organometallic Chemistry
Abstract
Abstract Reaction of 0.5 equiv. of trans-5-decene-3,7-diyne with W(CEt)(OCMe3)3 yields trans-(Me3CO)3WCCHCHCW(OCMe3)3 (2) via the intermediate trans-(Me3CO)3WCCHCHCCEt (1), while reaction of 1 equiv. of cis-5-decene-3,7-diyne with W(CEt)(OCMe3)3 yields cis,cis-(Me3CO)3WCCHCHCCCHCHCW(OCMe3)3 (4) via cis-(Me3CO)3WCCHCHCCEt (3). Reaction of additional cis- or trans-5-decene-3,7-diyne with either 2 and/or 4 results in decomposition. Bipyridyl adducts of related metal-capped oligomers have been prepared and are more stable, but they are too insoluble to serve as intermediates in polymerization reactions. Reaction of 0.5 equiv. of 1,4-dibutynylbenzene with W(CEt)(OCMe3)3 yields (Me3CO)3WC(1,4-C6H4)CW(OCMe3), while reaction of 1 equiv. of 1,2-dipentynylbenzene with W(CEt)(OCMe3)3 yields (Me3CO)3WC(1,2-C6H4)CC(1,2-C6H4)CW(OCMe3)3. Addition of 4 or more equiv. of 1,4-dibutynyl- or 1,2-dipentynyl-benzene to W(CEt)(OCMe3)3 results in formation of a yellow intractable product in less than 50% yield. It appears that either instability or insolubility of the growing polymers in this general class will limit their utility as catalysts.