Stereoselective Ring Expansion Metathesis Polymerization with Cationic Molybdenum Alkylidyne N-Heterocyclic Carbene Complexes.

Molybdenum alkylidyne -heterocyclic carbene (NHC) complexes of the type [Mo(C--CHY)(OC(R)(CF)) (L)(NHC)][B(Ar)] (Y = OMe, NO; R = CH, CF; L = none, pivalonitrile, tetrahydrofuran; NHC = 1,3-dimesitylimidazol-2-ylidene (IMes), 1,3-dimesityl-3,4-dihydroimidazol-2-ylidene (IMesH), 1,3-dimesityl-3,4-dichloroimidazol-2-ylidene (IMesCl), 1,3-diisopropylimidazol-2-ylidene (IPr); B(Ar) = tetrakis(3,5-bis(trifluoromethyl)phen-1-yl)borate) were used in the ring expansion metathesis polymerization (REMP) of cyclic olefins. With -cyclooctene (COE) cyclic, low molecular weight oligomers were obtained at low monomer concentrations and the cyclic nature of the polymer was confirmed by MALDI-TOF measurements. High-molecular weight cyclic poly(COE) became available at high monomer concentrations. Also, post-REMP allowed for converting low-molecular-weight cyclic poly(cCOE) into high-molecular-weight cyclic poly(cCOE). Tailored catalysts together with suitable additives offered access to the stereoselective REMP of functional norbornenes providing functional -isotactic (), -syndiotactic () and poly(norbornene)s with up to 99% stereoselectivity. Mechanistic details supported by density functional theory (DFT) calculations are outlined.