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Boryl−Metal Bonds Facilitate Cobalt/Nickel-Catalyzed Olefin Hydrogenation

Lin, Tzu-Pin and Peters, Jonas C. (2014) Boryl−Metal Bonds Facilitate Cobalt/Nickel-Catalyzed Olefin Hydrogenation. Journal of the American Chemical Society, 136 (39). pp. 13672-13683. ISSN 0002-7863. http://resolver.caltech.edu/CaltechAUTHORS:20140926-131812982

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Abstract

New approaches toward the generation of late first-row metal catalysts that efficiently facilitate two-electron reductive transformations (e.g., hydrogenation) more typical of noble-metal catalysts is an important goal. Herein we describe the synthesis of a structurally unusual S = 1 bimetallic Co complex, [(^(Cy)PBP)CoH]_2 (1), supported by bis(phosphino)boryl and bis(phosphino)hydridoborane ligands. This complex reacts reversibly with a second equivalent of H_2 (1 atm) and serves as an olefin hydrogenation catalyst under mild conditions (room temperature, 1 atm H_2). A bimetallic Co species is invoked in the rate-determining step of the catalysis according to kinetic studies. A structurally related Ni^INi^I dimer, [(^(Ph)PBP)Ni]_2 (3), has also been prepared. Like Co catalyst 1, Ni complex 3 displays reversible reactivity toward H_2, affording the bimetallic complex [(^(Ph)PBHP)NiH]_2 (4). This reversible behavior is unprecedented for Ni^I species and is attributed to the presence of a boryl–Ni bond. Lastly, a series of monomeric (^(tBu)PBP)NiX complexes (X = Cl (5), OTf (6), H (7), OC(H)O (8)) have been prepared. The complex (^(tBu)PBP)NiH (7) shows enhanced catalytic olefin hydrogenation activity when directly compared with its isoelectronic/isostructural analogues where the boryl unit is substituted by a phenyl or amine donor, a phenomenon that we posit is related to the strong trans influence exerted by the boryl ligand.


Item Type:Article
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URLURL TypeDescription
http://pubs.acs.org/doi/abs/10.1021/ja504667fPublisherArticle
http://dx.doi.org/10.1021/ja504667fDOIArticle
http://pubs.acs.org/doi/suppl/10.1021/ja504667fRelated ItemSupporting Information
ORCID:
AuthorORCID
Lin, Tzu-Pin0000-0001-7041-7213
Peters, Jonas C.0000-0002-6610-4414
Additional Information:© 2014 American Chemical Society. Received: May 9, 2014. Publication Date (Web): September 2, 2014. This material is based upon work performed by the Joint Center for Artificial Photosynthesis, a DOE Energy Innovation Hub supported through the Office of Science of the U.S. Department of Energy under Award DE-SC0004993. We thank Dr. David C. Leitch, Dr. Yichen Tan, and Dr. Charles C. McCrory for insightful discussions on kinetics. We also thank Prof. Gerard Parkin for insightful discussions on bonding.
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Funding AgencyGrant Number
Department of Energy (DOE)DE-SC0004993
Record Number:CaltechAUTHORS:20140926-131812982
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20140926-131812982
Official Citation:Boryl–Metal Bonds Facilitate Cobalt/Nickel-Catalyzed Olefin Hydrogenation Tzu-Pin Lin and Jonas C. Peters Journal of the American Chemical Society 2014 136 (39), 13672-13683
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:50069
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:26 Sep 2014 21:04
Last Modified:18 Apr 2017 18:03

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