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Reversible H_2 Addition across a Nickel−Borane Unit as a Promising Strategy for Catalysis

Harman, W. Hill and Peters, Jonas C. (2012) Reversible H_2 Addition across a Nickel−Borane Unit as a Promising Strategy for Catalysis. Journal of the American Chemical Society, 134 (11). pp. 5080-5082. ISSN 0002-7863. http://resolver.caltech.edu/CaltechAUTHORS:20120523-074508665

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Abstract

We report the synthesis and characterization of a series of nickel complexes of the chelating diphosphine-borane ligands ArB(o-Ph_2PC_6H_4)_2 ([^(Ar)DPB^(Ph)]; Ar = Ph, Mes). The [^(Ar)DPB^(Ph)] framework supports pseudo-tetrahedral nickel complexes featuring η^2-B,C coordination from the ligand backbone. For the B-phenyl derivative, the THF adduct [^(Ph)DPB^(Ph)]Ni(THF) has been characterized by X-ray diffraction and features a very short interaction between nickel and the η^2-B,C ligand. For the B-mesityl derivative, the reduced nickel complex [^(Mes)DPB^(Ph)]Ni is isolated as a pseudo-three-coordinate “naked” species that undergoes reversible, nearly thermoneutral oxidative addition of dihydrogen to give a borohydrido-hydride complex of nickel(II) which has been characterized in solution by multinuclear NMR. Furthermore, [^(Mes)DPB^(Ph)]Ni is an efficient catalyst for the hydrogenation of olefin substrates under mild conditions.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja211419t DOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja211419tPublisherArticle
Additional Information:© 2012 American Chemical Society. Received: December 6, 2011. Publication Date (Web): March 1, 2012. This work was supported by the NSF Center for Chemical Innovation: Powering the Planet grant CHE-0802907, and by the Gordon and Betty Moore Foundation. We thank Professor Greg Fu for a helpful suggestion.
Group:CCI Solar Fuels
Funders:
Funding AgencyGrant Number
NSF Center for Chemical InnovationCHE-0802907
Gordon and Betty Moore FoundationUNSPECIFIED
Record Number:CaltechAUTHORS:20120523-074508665
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20120523-074508665
Official Citation:Reversible H2 Addition across a Nickel–Borane Unit as a Promising Strategy for Catalysis W. Hill Harman and Jonas C. Peters Journal of the American Chemical Society 2012 134 (11), 5080-5082
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:31601
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:23 May 2012 15:07
Last Modified:04 Apr 2014 01:47

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