Buss, Joshua A. and Shida, Naoki and He, Tianyi and Agapie, Theodor (2021) Carbon Dioxide Reduction with Dihydrogen and Silanes at Low-Valent Molybdenum Terphenyl Diphosphine Complexes: Reductant Identity Dictates Mechanism. ACS Catalysis, 11 (21). pp. 13294-13302. ISSN 2155-5435. doi:10.1021/acscatal.1c02922. https://resolver.caltech.edu/CaltechAUTHORS:20211029-221513000
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Abstract
The reaction chemistry of both silanes and hydrogen at para-terphenyl diphosphine-supported molybdenum complexes was explored within the context of carbon dioxide (CO₂) reduction. CO₂ hydrosilylation commonly affords reduction products via silyl acetals. However, while silyl hydride complexes were characterized in the present system, synthetic, spectroscopic, and kinetic studies suggest C–O cleavage of CO₂ occurs independently of silanes. In their presence, a putative molybdenum oxo intermediate is hypothesized to undergo O-atom transfer, yielding silanol. In contrast, hydrogenation chemistry does occur through an intermediate molybdenum dihydride capable of inserting CO₂ to yield a formate hydride complex. This process is reversible; slow deinsertion under dinitrogen affords a mixture of molybdenum dihydride, η²-CO₂, and N₂ complexes. The molybdenum hydride formate species is a competent precatalyst for both CO₂ hydrogenation to formate (in the presence of lithium cations and base) and formic acid dehydrogenation to CO₂ and hydrogen (in the presence of base). Mechanistic studies of both catalytic processes are presented.
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Additional Information: | © 2021 American Chemical Society. Received: June 29, 2021; Revised: September 8, 2021. The authors thank Larry Henling and Mike Takase for crystallographic assistance and David VanderVelde for NMR expertise. The X-ray diffraction and NMR instrumentation were partially supported by the Dow Next Generation Educator Fund. T.A. is grateful for support from the NSF (CHE-1800501) for synthetic studies and DOE (Joint Center for Artificial Photosynthesis, Award Number DE-SC0004993) and King Fahd University of Petroleum and Minerals, Dhahran, Saudi Arabia (offered under the KFUPM-Caltech Research Collaboration) for CO₂ conversion studies. J.A.B. and N.S. are grateful for an NSF graduate research fellowship and a Grant-in-Aid for JSPS Research Fellows (No. 16J07350), respectively. Author Contributions: J.A.B. and N.S. contributed equally to this work. The authors declare no competing financial interest. | ||||||||||||||
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Subject Keywords: | CO2 reduction, hydrogen storage, formic acid dehydrogenation, hydrosilylation, molybdenum | ||||||||||||||
Issue or Number: | 21 | ||||||||||||||
DOI: | 10.1021/acscatal.1c02922 | ||||||||||||||
Record Number: | CaltechAUTHORS:20211029-221513000 | ||||||||||||||
Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20211029-221513000 | ||||||||||||||
Official Citation: | Carbon Dioxide Reduction with Dihydrogen and Silanes at Low-Valent Molybdenum Terphenyl Diphosphine Complexes: Reductant Identity Dictates Mechanism. Joshua A. Buss, Naoki Shida, Tianyi He, and Theodor Agapie. ACS Catalysis 2021 11 (21), 13294-13302; DOI: 10.1021/acscatal.1c02922 | ||||||||||||||
Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | ||||||||||||||
ID Code: | 111694 | ||||||||||||||
Collection: | CaltechAUTHORS | ||||||||||||||
Deposited By: | Tony Diaz | ||||||||||||||
Deposited On: | 02 Nov 2021 21:30 | ||||||||||||||
Last Modified: | 24 Nov 2021 18:40 |
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