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A d^10 Ni–(H_2) Adduct as an Intermediate in H-H Oxidative Addition across a Ni-B Bond

Harman, W. Hill and Lin, Tzu-Pin and Peters, Jonas 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 Edition, 53 (4). pp. 1081-1086. ISSN 1433-7851.

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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 H_2 activation reactions at late-metal boratranes and herein describe a diphosphine–borane-supported Ni—(H_2) complex, [(^(Ph)DPB^(iPr))Ni(H_2)], which has been characterized in solution. ^1H NMR spectroscopy confirms the presence of an intact H_2 ligand. A range of data, including electronic-structure calculations, suggests a d^(10) configuration for [(^(Ph)DPB^(iPr))Ni(H_2)] as most appropriate. Such a configuration is highly unusual among transition-metal H_2 adducts. The nonclassical H_2 adduct is an intermediate in the complete activation of H_2 across the Ni-B interaction. Reaction-coordinate analysis suggests synergistic activation of the H_2 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—(H_2) interaction and in the H—H cleavage step.

Item Type:Article
Related URLs:
URLURL TypeDescription
Lin, Tzu-Pin0000-0001-7041-7213
Peters, Jonas C.0000-0002-6610-4414
Additional Information:© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. Published online: December 9, 2013; Received: September 17, 2013. Supporting information for this article is available on the WWW under This research was supported by the NSF Center for Chemical Innovation: Solar Fuels (grant CHE-0802907) and by the Gordon and Betty Moore Foundation. We thank Prof. Christopher C. Cummins and Dr. Smith Nielsen for insightful discussions.
Group:CCI Solar Fuels
Funding AgencyGrant Number
Gordon and Betty Moore FoundationUNSPECIFIED
Subject Keywords:borane ligands; H_2 activation; H_2 complexes; nickel; reaction mechanisms
Issue or Number:4
Record Number:CaltechAUTHORS:20140213-154635896
Persistent URL:
Official Citation:Harman, W. H., Lin, T.-P. and Peters, J. C. (2014). A d^(10) Ni–(H_2) Adduct as an Intermediate in H-H Oxidative Addition across a Ni-B Bond. Angew. Chem. Int. Ed., 53(4), 1081–1086. doi: 10.1002/anie.201308175
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:43824
Deposited By: Bianca Rios
Deposited On:14 Feb 2014 22:06
Last Modified:03 Oct 2019 06:11

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