Metal catalysts for the vinyl/addition polymerization of norbornene

A full literature account is given on work describing the transition-metal catalyzed vinyl or addition polymerization to polynorbornene covering the years of 2001 to the beginning of 2008. The interest in vinyl polynorbornene is driven by its dielectric and mechanical properties for the technical application in microelectronics applications. Metal catalysts of Ti, Cr, Fe, Co, Ni, Pd and Cu with methylalumoxane (MAO) or perfluorinated borane, e.g. B(C6F5)3, cocatalysts are presented in terms of their activity and ligand effects. Among the ligands Schiff bases, tridentate N,N,N-bis(imino)pyridyl, bidentate N,N-anilido-imin, N,O-β-ketoiminato, N,O-salicylaldiminato (=salicylideneiminato), O,O-β-diketonato (=acetylacetonato), P,P-bis(phosphino)alkane, multidentate carbon ligands, e.g. allyl, cyclopentadienyl, aryl, and monodentate halo, especially chloro, triphenylphosphane (PPh3) and phenyl feature prominently.