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Living cyclopolymerization of diethyl dipropargylmalonate by Mo(CH-t-Bu)(NAr)[OCMe(CF{sub 3}){sub 2}]{sub 2} in dimethoxyethane

Journal Article · · Organometallics
;  [1]
  1. Massachusetts Institute of Technology, Cambridge, MA (United States)

Cyclopolymerization of diethyl dipropargylmalonate (1) by Mo(CH-t-Bu)(NAr)[OCMe(CF{sub 3}){sub 2}]{sub 2} (2) in dimethoxyethane (DME) proceeds in a living manner to give a conjugated polyene that contains both five- and six-membered rings incorporated into the polyene backbone. Cyclization to give the five-membered ring is believed to prevent deactivation of the catalyst. GPC analysis shows that poly(1){sub n} polymers have low polydispersities (M{sub w}/M{sub n} {le} 1.25) and values for M{sub n} that increase linearly with the amount of monomer employed. The living nature of the polymerization was also demonstrated by synthesis of a block copolymer from 20 equiv of 1 followed by 200 equiv of 2,3-dicarbomethoxynorbornadiene (5). 28 refs., 1 fig., 1 tab.

Sponsoring Organization:
USDOE
DOE Contract Number:
FG02-86ER13564
OSTI ID:
555000
Journal Information:
Organometallics, Journal Name: Organometallics Journal Issue: 8 Vol. 11; ISSN 0276-7333; ISSN ORGND7
Country of Publication:
United States
Language:
English