Synthesis of High Oxidation State Molybdenum Imido Heteroatom-Substituted Alkylidene Complexes
Author(s)Townsend, Erik M.; Kilyanek, Stefan M.; Smith, Stacey J.; Hoveyda, Amir H.; Schrock, Richard Royce; Mueller, Peter; ... Show more Show less
High Oxidation State Molybdenum Imido Heteroatom-Substituted Alkylidene Complexes
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Reactions between Mo(NAr)(CHR)(Me[subscript 2]Pyr)(OTPP) (Ar = 2,6-i-Pr[subscript 2]C[subscript 6]H[subscript 3], R = H or CHCMe[subscript 2]Ph, Me[subscript 2]Pyr = 2,5-dimethylpyrrolide, OTPP = O-2,3,5,6-Ph[subscript 4]C[subscript 6]H) and CH[subscript 2]═CHX where X = B(pin), SiMe[subscript 3], N-carbazolyl, N-pyrrolidinonyl, PPh[subscript 2], OPr, or SPh lead to Mo(NAr)(CHX)(Me[subscript 2]Pyr)(OTPP) complexes in good yield. All have been characterized through X-ray studies (as an acetonitrile adduct in the case of X = PPh[subscript 2]). The efficiencies of metathesis reactions initiated by Mo(NAr)(CHX)(Me[subscript 2]Pyr)(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.
DepartmentMassachusetts Institute of Technology. Department of Chemistry
American Chemical Society (ACS)
Townsend, Erik M., Stefan M. Kilyanek, Richard R. Schrock, Peter Mueller, Stacey J. Smith, and Amir H. Hoveyda. “High Oxidation State Molybdenum Imido Heteroatom-Substituted Alkylidene Complexes.” Organometallics 32, no. 16 (August 26, 2013): 4612–4617.
Author's final manuscript