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Reduction of Nitriles to Amines with H 2 Catalyzed by Nonclassical Ruthenium Hydrides – Water‐Promoted Selectivity for Primary Amines and Mechanistic Investigations
Author(s) -
Gunanathan Chidambaram,
Hölscher Markus,
Leitner Walter
Publication year - 2011
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201100392
Subject(s) - chemistry , ruthenium , nitrile , hydride , selectivity , catalysis , pincer movement , pincer ligand , ligand (biochemistry) , primary (astronomy) , photochemistry , medicinal chemistry , combinatorial chemistry , hydrogen , organic chemistry , biochemistry , physics , receptor , astronomy
Catalytic hydrogenation of nitriles to amines by nonclassical ruthenium hydride complexes derived from PNP pincer ligands is described. Aromatic as well as aliphatic nitriles are reduced to the corresponding primary amines. Hydrogen pressure influences the selectivity for the primary amines. The mechanism of nitrile reduction with nonclassical ruthenium hydride pincer complexes is investigated by DFT calculations. A catalytic cycle involving the coordination of nitrile trans to the pincer backbone after an initial hydride rearrangement at the ruthenium center, and the subsequent first transfer of the hydride ligand to the carbon center of the nitrile ligand is suggested as a possible reaction mechanism. Interestingly, the use of water as additive increases the selectivity for the primary amines and the rate of the reactions.