Bipyridine Adducts of Molybdenum Imido Alkylidene and Imido Alkylidyne Complexes
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Schrock_Bipyridine adducts.pdf
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Author(s)
Lichtscheidl, Alejandro G.
Ng, Victor Wee Lin
Takase, Michael K.
Malcolmson, Steven J.
Meek, Simon J.
Li, Bo
Kiesewetter, Elizabeth T.
Hoveyda, Amir H.
Muller, Peter
Schrock, Richard Royce
Date Issued
June 2012
Journal
Organometallics
Publisher
American Chemical Society (ACS)
Citation
Lichtscheidl, Alejandro G., Victor W. L. Ng, Peter Müller, Michael K. Takase, Richard R. Schrock, Steven J. Malcolmson, Simon J. Meek, Bo Li, Elizabeth T. Kiesewetter, and Amir H. Hoveyda. “Bipyridine Adducts of Molybdenum Imido Alkylidene and Imido Alkylidyne Complexes.” Organometallics 31, no. 12 (June 25, 2012): 4558-4564.
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Author's final manuscript
Abstract
Seven bipyridine adducts of molybdenum imido alkylidene bispyrrolide complexes of the type Mo(NR)(CHCMe[subscript 2]R′)(Pyr)[subscript 2](bipy) (1a–1g; R = 2,6-i-Pr[subscript 2]C[subscript 6]H[subscript 3] (Ar), adamantyl (Ad), 2,6-Me[subscript 2]C[subscript 6]H[subscript 3] (Ar′), 2-i-PrC[subscript 6]H[subscript 4] (Ar[superscript iPr]), 2-ClC[subscript 6]H[subscript 4] (Ar[superscript Cl]), 2-t-BuC[subscript 6]H[subscript 4] (Ar[superscript tBu]), and 2-MesitylC[subscript 6]H[subscript 4] (Ar[superscript M]), respectively; R′ = Me, Ph) have been prepared using three different methods. Up to three isomers of the adducts are observed that are proposed to be the trans- and two possible cis-pyrrolide isomers of syn-alkylidenes. Sonication of a mixture containing 1a–1g, HMTOH (2,6-dimesitylphenol), and ZnCl[subscript 2](dioxane) led to the formation of MAP species of the type Mo(NR)(CHCMe[subscript 2]R′)(Pyr)(OHMT) (3a–3g). DCMNBD (2,3-dicarbomethoxynorbornadiene) is polymerized employing 3a–3g as initiators to yield >98% cis,syndiotactic poly(DCMNBD). Attempts to prepare bipy adducts of bisdimethylpyrrolide complexes led to the formation of imido alkylidyne complexes of the type Mo(NR)(CCMe[subscript 2]R′)(Me[subscript 2]Pyr)(bipy) (Me[subscript 2]Pyr = 2,5-dimethylpyrrolide; 4a–4g) through a ligand-induced migration of an alkylidene α proton to a dimethylpyrrolide ligand. X-ray structures of Mo(NAr)(CHCMe[subscript 2]Ph)(Pyr)[subscript 2](bipy) (1a), Mo(NAr[superscript iPr])(CHCMe[subscript 2]Ph)(Pyr)(OHMT) (3d), Mo(NAr)(CCMe[subscript 2]Ph)(Me[subscript 2]Pyr)(bipy) (4a), the NAr′ analog of 4a (4c), and Mo(NAr[superscript T])(CCMe[subscript 3])(Me[subscript 2]Pyr)(bipy) (Ar[superscript T] = 2-(2,4,6-i-Pr[subscript 3]C[subscript 6]H[subscript 2])C[subscript 6]H[subscript 4]; 4g) showed normal bond lengths and angles.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
https://doi.org/10.1021/om300353e
