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Z-Selective Semihydrogenation of Alkynes Catalyzed by a Cationic Vanadium Bisimido Complex

Authors

  • Henry S. La Pierre,

    1. Department of Chemistry, University of California, Berkeley, CA 94720 (USA), Fax: (+1) 510-666-2504
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  • Prof. Dr. John Arnold,

    Corresponding author
    1. Department of Chemistry, University of California, Berkeley, CA 94720 (USA), Fax: (+1) 510-666-2504
    • Department of Chemistry, University of California, Berkeley, CA 94720 (USA), Fax: (+1) 510-666-2504===

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  • Prof. Dr. F. Dean Toste

    Corresponding author
    1. Department of Chemistry, University of California, Berkeley, CA 94720 (USA), Fax: (+1) 510-666-2504
    • Department of Chemistry, University of California, Berkeley, CA 94720 (USA), Fax: (+1) 510-666-2504===

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  • The NIH GMS (R01 GM074774) and NSF (CHE 0848931) are gratefully acknowledged for financial support. We thank Drs. A. Pasquale, C. Canlas, and J. Krinsky for experimental assistance, Profs. R. G. Bergman and S. B. Duckett for helpful discussions, and Prof. A. Pines for a donation of para-H2. H.S.La.P. is grateful to the NSF for a pre-doctoral fellowship and the UCB Department of Chemistry for the Dauben Fellowship.

Abstract

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Early metal gets the H: Under 1 atm of H2, the vanadium complex 1 (PFTB=perfluoro-tert-butoxide) catalytically semihydrogenates alkynes to Z alkenes. Synthetic and DFT studies, in combination with H2/D2 and NMR experiments, indicate that H2 is activated by 1,2-addition to 1. Upon insertion of an alkyne into the V[BOND]H bond of A, the product alkene and 1 are generated by the 1,2-α-NH-elimination of the alkenyl ligand.

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