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Transfer Hydrogenation of Unsaturated Substrates by Half‐sandwich Ruthenium Catalysts using Ammonium Formate as Reducing Reagent
Author(s) -
Mai Van Hung,
Lee SanHwa,
Nikonov Georgii I.
Publication year - 2017
Publication title -
chemistryselect
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.437
H-Index - 34
ISSN - 2365-6549
DOI - 10.1002/slct.201701423
Subject(s) - phosphine , catalysis , chemistry , ammonium formate , ruthenium , reagent , formate , transfer hydrogenation , ammonium , medicinal chemistry , organic chemistry , acetonitrile
A series of half‐sandwich phosphine‐ and NHC‐supported complexes were screened in catalytic transfer hydrogenation of nitriles, N ‐heterocycles, olefins, and carbonyls by using ammonium formate as the reductant. Complex [Cp( i Pr 3 P)Ru(NCCH 3 ) 2 ][PF 6 ] ( 3 ) was found to be the most efficient catalyst. Mechanistic studies suggested that the formate complexes Cp( i Pr 3 P)Ru(κ 2 ‐O 2 CH) and Cp( i Pr 3 P)Ru(κ 1 ‐O 2 CH)(NCCH 3 ) could be the true catalysts in these reactions. An inner‐sphere monohydride mechanism was suggested. Excess free phosphine impedes the catalysis by forming the catalytically inactive bis(phosphine) complex Cp( i Pr 3 P) 2 RuH.