ACYCLIC DIENE METATHESIS (ADMET) POLYMERIZATION USING ARYLOXY TUNGSTEN-BASED CLASSICAL CATALYTIC-SYSTEMS

The range of ADMET polymerization active catalysts has been expanded t o include classical catalytic systems. The acyclic diene metathesis (A DMET) polymerization of hydrocarbon dienes has been performed using th e aryloxy-tungsten complexes WCl4(O-2,6-C6H3Ph2)(2) (4), W(O)Cl-2(O-2, 6-C6H3Br2)(2) (5) and WCl4(O-2,6-C6H3Br2)(2) (6) as the precatalytic s pecies in combination with tetrabutyltin, tetramethyltin and tri-n-but yltin hydride as the cocatalytic entities. High molecular weight polyo ctenylene and polyheptenylene are obtained under bulk polymerization c onditions. The scope of these classical metathesis catalysts in the po lymerization of other hydrocarbon as well as functionalized dienes is studied, revealing significant reactivity differences with respect to the previously studied well-defined metathesis catalysts and providing insights into the identification of suitable classical systems for AD MET polymerization.