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Oxidative Addition of Ammonia to Form a Stable Monomeric Amido Hydride Complex

Author:
Zhao, Jing, Goldman, Alan S., Hartwig, John F.
Source:
Science 2005 v.307 no.5712 pp. 1080-1082
ISSN:
0036-8075
Subject:
ambient temperature, ammonia, carbon, chemical bonding, hydrides, iridium, isotope labeling, ligands, olefin, phosphorus
Abstract:
The insertion of an iridium complex into an N-H bond in ammonia leads to a stable monomeric amido hydride complex in solution at room temperature. This reaction advances the transition-metal coordination chemistry of ammonia beyond its role for more than a century as an ancillary ligand. The precursor for this insertion reaction is an iridium(I) olefin complex with an aliphatic ligand containing one carbon and two phosphorus donor atoms. Kinetic and isotopic labeling studies indicate that olefin dissociates to give a 14-electron iridium(I) fragment, which then reacts with ammonia. This cleavage of the N-H bond under neutral conditions provides a foundation on which to develop future mild catalytic transformations of ammonia, such as olefin hydroamination and arene oxidative amination.
Agid:
1530241