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Z ‐Selective Semihydrogenation of Alkynes Catalyzed by a Cationic Vanadium Bisimido Complex
Author(s) -
La Pierre Henry S.,
Arnold John,
Toste F. Dean
Publication year - 2011
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201007876
Subject(s) - vanadium , alkyne , cationic polymerization , alkene , catalysis , chemistry , ligand (biochemistry) , medicinal chemistry , metal , polymer chemistry , organic chemistry , biochemistry , receptor
Early metal gets the H : Under 1 atm of H 2 , the vanadium complex 1 (PFTB=perfluoro‐ tert ‐butoxide) catalytically semihydrogenates alkynes to Z alkenes. Synthetic and DFT studies, in combination with H 2 /D 2 and NMR experiments, indicate that H 2 is activated by 1,2‐addition to 1 . Upon insertion of an alkyne into the VH bond of A , the product alkene and 1 are generated by the 1,2‐α‐NH‐elimination of the alkenyl ligand.