Metathesis polymerisation of phenylacetylene catalysed by (arene)Mo(CO)3 activated by electron acceptor chloranil

Phenylacetylene (PA) was polymerised by employing (arene)Mo(CO)3/chloranil mixture as the catalyst. Preliminary kinetic studies of the polymerisation showed the presence of an induction period before commencement of polymerisation, attributable to the activation of the (arene)Mo(CO)3 by chloranil through charge-transfer. It was shown that better control over polymer molecular weight and polydispersity was achieved with prior mixing of the metal carbonyl complex with the acceptor and by delaying the addition of the monomer. Polymerisation by metathesis route was ascertained by copolymerisation, sequential addition of monomers and also by end-capping reactions.