Complexes of general formula [(Cy 2 P(CH 2 ) n PCy 2 )Ru(η 3 -C 4 H 7 ) 2 ] ( n = 1−3) are halide-free initiators for ring-opening metathesis polymerization (ROMP) of norbornene. The chain length of the chelating phosphine exhibits an effect on the polymer yield and the stereochemistry at the C C double bond. Analysis of the resulting polymer by GPC and electron microscopy indicates an initiation efficiency of approximately 10%. A mechanism for the formation of the propagating species is proposed that involves merging of the two allyl moieties and cycloreversion of the resulting ruthenacyclobutane to give a carbene intermediate containing a cis -PRuP chelate ring.
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Six et al. (2000) studied this question.
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