Synthesis of High Oxidation State Molybdenum Imido Heteroatom-Substituted Alkylidene Complexes
Name
Schrock_High oxidation.pdf
Size
1.53 MB
Format
Adobe PDF
Checksum (MD5)
e8ccccbe5ef1921cebe28649badb8e05
Author(s)
Townsend, Erik M.
Kilyanek, Stefan M.
Smith, Stacey J.
Hoveyda, Amir H.
Schrock, Richard Royce
Mueller, Peter
Alternative Title
High Oxidation State Molybdenum Imido Heteroatom-Substituted Alkylidene Complexes
Date Issued
August 2013
Journal
Organometallics
Publisher
American Chemical Society (ACS)
Citation
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.
Version
Author's final manuscript
Abstract
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.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
Terms of Use
Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use.
Persistent DSpace Link
DOI of Published Version
https://doi.org/10.1021/om400584f
