Abstract

Rh + (2,5-norbornadiene)[(η 6 -C 6 H 5 )B - (C 6 H 5 ) 3 ], a zwitterionic Rh(I) complex, shows excellent activity for the polymerization of monosubstituted acetylenes under mild conditions. The reaction of phenylacetylene and its p- and m-substituted derivatives proceeds rapidly to give yellow soluble polymers with a cis configuration of the main polymer chain and with a high number-average molecular weight (>10 5 ) in high yields. The o-substituted derivatives give stereoregular red crystalline polymers which are scarcely soluble in organic solvents. The Rh complex has a moderate activity for the polymerization of tert-butylacetylene, cyclohexylacetylene, and 3-ethyl-1-pentyne to afford stereoregular cis polymers in quantitative yields.

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