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. https://resolver.caltech.edu/CaltechAUTHORS:20140926-131812982
|
PDF
- Supplemental Material
See Usage Policy. 2491Kb | |
![]() |
Crystallographic Info File (CIF) (CIF)
- Supplemental Material
See Usage Policy. 464Kb |
Use this Persistent URL to link to this item: https://resolver.caltech.edu/CaltechAUTHORS:20140926-131812982
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 | ||||||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|
Related URLs: |
| ||||||||||||
ORCID: |
| ||||||||||||
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. | ||||||||||||
Funders: |
| ||||||||||||
Issue or Number: | 39 | ||||||||||||
Record Number: | CaltechAUTHORS:20140926-131812982 | ||||||||||||
Persistent URL: | https://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: | 03 Oct 2019 07:20 |
Repository Staff Only: item control page