Synthesis of High Oxidation State Molybdenum Imido Heteroatom-Substituted Alkylidene Complexes

Reactions between Mo(NAr)(CHR)(Me2Pyr)(OTPP) (Ar = 2,6-i-Pr2C6H3, R = H or CHCMe2Ph, Me2Pyr = 2,5-dimethylpyrrolide, OTPP = O-2,3,5,6-Ph4C6H) and CH2═CHX where X = B(pin), SiMe3, N-carbazolyl, N-pyrrolidinonyl, PPh2, OPr, or SPh lead to Mo(NAr)(CHX)(Me2Pyr)(OTPP) complexes in good yield. All have been characterized through X-ray studies (as an acetonitrile adduct in the case of X = PPh2). The efficiencies of metathesis reactions initiated by Mo(NAr)(CHX)(Me2Pyr)(OTPP) complexes can be rationalized on the basis of steric factors; electronic differences imposed as a consequence of X being bound to the alkylidene carbon do not seem to play a major role. Side reactions that promote catalyst decomposition do not appear to be a serious limitation for Mo═CHX species.