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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.

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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 ItemSupporting Information
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.
Funding AgencyGrant Number
Department of Energy (DOE)DE-SC0004993
Issue or Number:39
Record Number:CaltechAUTHORS:20140926-131812982
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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
Deposited By: Ruth Sustaita
Deposited On:26 Sep 2014 21:04
Last Modified:03 Oct 2019 07:20

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