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Harman WH, Lin TP, Peters JC. A d(10) Ni-(H(2)) adduct as an intermediate in H-H oxidative addition across a Ni-B bond. Angew Chem Int Ed Engl. 2013;53(4):1081-6doi: 10.1002/anie.201308175.
Harman, W. H., Lin, T. P., & Peters, J. C. (2014). A d(10) Ni-(H(2)) adduct as an intermediate in H-H oxidative addition across a Ni-B bond. Angewandte Chemie (International ed. in English), 53(4), 1081-6. https://doi.org/10.1002/anie.201308175
Harman, W Hill, et al. "A d(10) Ni-(H(2)) adduct as an intermediate in H-H oxidative addition across a Ni-B bond." Angewandte Chemie (International ed. in English) vol. 53,4 (2014): 1081-6. doi: https://doi.org/10.1002/anie.201308175
Harman WH, Lin TP, Peters JC. A d(10) Ni-(H(2)) adduct as an intermediate in H-H oxidative addition across a Ni-B bond. Angew Chem Int Ed Engl. 2014 Jan 20;53(4):1081-6. doi: 10.1002/anie.201308175. Epub 2013 Dec 09. PMID: 24323761.
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Angew Chem Int Ed Engl. 2014 Jan 20;53(4):1081-6. doi: 10.1002/anie.201308175. Epub 2013 Dec 09.

A d(10) Ni-(H(2)) adduct as an intermediate in H-H oxidative addition across a Ni-B bond.

Angewandte Chemie (International ed. in English)

W Hill Harman, Tzu-Pin Lin, Jonas C Peters

Affiliations

  1. Division of Chemistry and Chemical Engineering, California Institute of Technology (USA); Current address: Department of Chemistry, University of California, Riverside, CA 92521 (USA).

PMID: 24323761 DOI: 10.1002/anie.201308175

Abstract

Bifunctional EH activation offers a promising approach for the design of two-electron-reduction catalysts with late first-row metals, such as Ni. To this end, we have been pursuing H2 activation reactions at late-metal boratranes and herein describe a diphosphine-borane-supported Ni-(H2 ) complex, [((Ph) DPB(iPr) )Ni(H2 )], which has been characterized in solution. (1) H NMR spectroscopy confirms the presence of an intact H2 ligand. A range of data, including electronic-structure calculations, suggests a d(10) configuration for [((Ph) DPB(iPr) )Ni(H2 )] as most appropriate. Such a configuration is highly unusual among transition-metal H2 adducts. The nonclassical H2 adduct is an intermediate in the complete activation of H2 across the NiB interaction. Reaction-coordinate analysis suggests synergistic activation of the H2 ligand by both the Ni and B centers of the nickel boratrane subunit, thus highlighting an important role of the borane ligand both in stabilizing the d(10) Ni-(H2 ) interaction and in the H-H cleavage step.

Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Keywords: H2 activation; H2 complexes; borane ligands; nickel; reaction mechanisms

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