On the Origin of E-Selectivity in the Ring-Opening Metathesis Polymerization with Molybdenum Imido Alkylidene N-Heterocyclic Carbene Complexes

[Image: see text] The understanding and control of stereoselectivity is a central aspect in ring-opening metathesis polymerization (ROMP). Herein, we report detailed quantum chemical studies on the reaction mechanism of E-selective ROMP of norborn-2-ene (NBE) with Mo(N-2,6-Me(2)-C(6)H(3))(CHCMe(3))(IMes)(OTf)(2) (1, IMes = 1,3-dimesitylimidazol-2-ylidene) as a first step to stereoselective polymerization. Four different reaction pathways based on an ene(syn) or ene(anti) approach of NBE to either the syn- or anti-isomer of the neutral precatalyst have been studied. In contrast to the recently established associative mechanism with a terminal alkene, where a neutral olefin adduct is formed, NBE reacts directly with the catalyst via [2 + 2] cycloaddition to form molybdacyclobutane with a reaction barrier about 30 kJ mol(–1) lower in free energy than via the formation of a catalyst–monomer adduct. However, the direct cycloaddition of NBE was only found for one out of four stereoisomers. Our findings strongly suggest that this stereoselective approach is responsible for E-selectivity and point toward a substrate-specific reaction mechanism in olefin metathesis with neutral Mo imido alkylidene N-heterocyclic carbene bistriflate complexes.