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Wiley, Angewandte Chemie International Edition, 17(50), p. 3900-3903, 2011

DOI: 10.1002/anie.201007876

Wiley, Angewandte Chemie, 17(123), p. 3986-3989, 2011

DOI: 10.1002/ange.201007876

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

Journal article published in 2011 by Henry S. La Pierre, John Arnold ORCID, F. Dean Toste, F. Dean Toste
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This paper is available in a repository.

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Abstract

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/D 2 and NMR experiments, indicate that H2 is activated by 1,2-addition to 1. Upon insertion of an alkyne into the V-H bond of A, the product alkene and 1 are generated by the 1,2-α-NH-elimination of the alkenyl ligand.