Oxidative Addition of Ammonia to Form a Stable Monomeric Amido Hydride Complex
Top Cited Papers
- 18 February 2005
- journal article
- other
- Published by American Association for the Advancement of Science (AAAS) in Science
- Vol. 307 (5712) , 1080-1082
- https://doi.org/10.1126/science.1109389
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.Keywords
This publication has 19 references indexed in Scilit:
- Synthesis and Reactivity of a Mononuclear Parent Amido Nickel Complex. Structures of Ni[C6H3-2,6-(CH2PiPr2)2](NH2) and Ni[C6H3-2,6-(CH2PiPr2)2](OMe)Organometallics, 2004
- Synthesis and Reactivity of a Coordinatively Unsaturated Ruthenium(II) Parent Amido Complex: Studies of X−H Activation (X = H or C)Organometallics, 2004
- C−H Oxidative Addition with a (PCP)Ir(III)-Pincer ComplexOrganometallics, 2002
- Oxidative Addition of Water by an Iridium PCP Pincer Complex: Catalytic Dehydrogenation of Alkanes by IrH(OH){C6H3-2,6-(CH2PBut2)2}Organometallics, 2001
- Addition of C−H Bonds to the Catalytically Active Complex (PCP)Ir (PCP = η3-2,6-(tBu2PCH2)2C6H3)Journal of the American Chemical Society, 2000
- Monomeric Cyclopentadienylnickel Methoxo and Amido Complexes: Synthesis, Characterization, Reactivity, and Use for Exploring the Relationship between H−X and M−X Bond EnergiesJournal of the American Chemical Society, 1997
- Synthesis and Reactivity of [IrH2(tBu2P)CH2CH2CHCH2CH2P(tBu2)], a Dynamic Iridium Polyhydride ComplexOrganometallics, 1994
- Theoretical study of the structures of electron-deficient d6 ML5 complexes. Importance of a .pi.-donating ligandOrganometallics, 1992
- Monomeric metal hydroxides, alkoxides, and amides of the late transition metals: synthesis, reactions, and thermochemistryChemical Reviews, 1988
- Nitrogen-hydrogen activation. 1. Oxidative addition of ammonia to iridium(I). Isolation, structural characterization and reactivity of amidoiridium hydridesInorganic Chemistry, 1987