Temperature and Solvent Effects on H2 Splitting and Hydricity: Ramifications on CO2 Hydrogenation by a Rhenium Pincer Catalyst

Hu, Jenny; Bruch, Quinton J.; Miller, Alexander M.

doi:10.1021/jacs.0c11110

Title: Temperature and Solvent Effects on H₂ Splitting and Hydricity: Ramifications on CO₂ Hydrogenation by a Rhenium Pincer Catalyst

Journal Article · Thu Dec 31 00:00:00 EST 2020 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.0c11110· OSTI ID:1782420

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Univ. of North Carolina, Chapel Hill, NC (United States)

The catalytic hydrogenation of carbon dioxide holds immense promise for applications in sustainable fuel synthesis and hydrogen storage. Mechanistic studies that connect thermodynamic parameters with the kinetics of catalysis can provide new understanding and guide predictive design of improved catalysts. Reported here are thermochemical and kinetic analyses of a new pincer-ligated rhenium complex (^tBuPOCOP)Re(CO)₂ (^tBuPOCOP = 2,6-bis(di-tert-butylphosphinito)phenyl) that catalyzes CO₂ hydrogenation to formate with faster rates at lower temperature. Because the catalyst follows the prototypical “outer sphere” hydrogenation mechanism, comprehensive studies of temperature and solvent effects on the H₂ splitting and hydride transfer steps are expected to be relevant to many other catalysts. Strikingly large entropy associated with cleavage of H2 results in a strong temperature dependence on the concentration of [(^tBuPOCOP)Re(CO)₂H]^– present during catalysis, which is further impacted by changing the solvent from toluene to tetrahydrofuran to acetonitrile. New methods for determining the hydricity of metal hydrides and formate at temperatures other than 298 K were developed, providing insight into how temperature can influence the favorability of hydride transfer during catalysis. These thermochemical insights guided the selection of conditions for CO₂ hydrogenation to formate with high activity (up to 364 h^–1 at 1 atm or 3330 h^–1 at 20 atm of 1:1 H₂ CO₂). In cases where hydride transfer is the highest individual kinetic barrier, entropic contributions to outer sphere H₂ splitting lead to a unique temperature dependence: catalytic activity increases as temperature decreases in tetrahydrofuran (200-fold increase upon cooling from 50 to 0 °C) and toluene (4-fold increase upon cooling from 100 to 50 °C). Furthermore, the ramifications on catalyst structure-function relationships are discussed, including comparisons between “outer sphere” mechanisms and metal–ligand cooperation mechanisms.

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Research Organization:: University of North Carolina, Chapel Hill, NC (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: SC0014255; CHE-1726291; CHE-1828183

OSTI ID:: 1782420

Journal Information:: Journal of the American Chemical Society, Vol. 143, Issue 2; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: Temperature and Solvent Effects on H2 Splitting and Hydricity: Ramifications on CO2 Hydrogenation by a Rhenium Pincer Catalyst

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Title: Temperature and Solvent Effects on H₂ Splitting and Hydricity: Ramifications on CO₂ Hydrogenation by a Rhenium Pincer Catalyst