LIVING CYCLOPOLYMERIZATION OF DIETHYL DIPROPARGYLMALONATE BY MO(CH-T-BU)(NAR)[OCME(CF3)2]2 IN DIMETHOXYETHANE

被引:145
作者
FOX, HH [1 ]
SCHROCK, RR [1 ]
机构
[1] MIT,DEPT CHEM 6-331,CAMBRIDGE,MA 02139
关键词
D O I
10.1021/om00044a012
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Cyclopolymerization of diethyl dipropargylmalonate (1) by Mo(CH-t-Bu)(NAr)[OCMe(CF3)2]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)n polymers have low polydispersities (M(w)/M(n) less-than-or-equal-to 1.25) and values for M(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).
引用
收藏
页码:2763 / 2765
页数:3
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