Visible-Light-Enhanced Cobalt-Catalyzed Hydrogenation: Switchable Catalysis Enabled by Divergence between Thermal and Photochemical Pathways

Mendelsohn, Lauren N.; MacNeil, Connor S.; Tian, Lei; Park, Yoonsu; Scholes, Gregory D.; Chirik, Paul J.

doi:10.1021/acscatal.0c05136

Title: Visible-Light-Enhanced Cobalt-Catalyzed Hydrogenation: Switchable Catalysis Enabled by Divergence between Thermal and Photochemical Pathways

Journal Article · Wed Jan 13 00:00:00 EST 2021 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.0c05136· OSTI ID:1760172

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Princeton Univ., NJ (United States)

The catalytic hydrogenation activity of the readily-prepared, coordinatively saturated cobalt(I) precatalyst, (R,R)-(^iPrDuPhos)Co(CO)₂H ((R,R)-^iPrDuPhos = (+)-1,2-bis[(2R,5R)-2,5-diisopropylphospholano]benzene) is described. While efficient turnover was observed with a range of alkenes upon heating to 100 ºC, the catalytic performance of the cobalt catalyst was markedly enhanced upon irradiation with blue light at 35 °C. Here, this improved reactivity enabled hydrogenation of terminal, di- and trisubstituted alkenes, alkynes, and carbonyl compounds. A combination of deuterium labeling studies, hydrogenation of alkenes containing radical clocks and experiments probing relative rates support a hydrogen atom transfer pathway under thermal conditions that is enabled by a relatively weak cobalt–hydrogen bond of 56 kcal/mol. In contrast, data for the photocatalytic reactions support light-induced dissociation of a carbonyl ligand followed by a coordination-insertion sequence where the product is released by combination of a cobalt alkyl intermediate with the starting hy-dride, (R,R)-(^iPrDuPhos)Co(CO)₂H. These results demonstrate the versatility with catalysis with Earth-abundant metals as pathways involving open- versus closed-shell intermediates can be switched by the energy source.

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Research Organization:: Princeton Univ., NJ (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0006498

OSTI ID:: 1760172

Journal Information:: ACS Catalysis, Vol. 11; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Cobalt
hydrogenation
switchable mechanism
radicals
visible light
alkene
hydrocarbons
styrenes
catalytic reactions
irradiation

Title: Visible-Light-Enhanced Cobalt-Catalyzed Hydrogenation: Switchable Catalysis Enabled by Divergence between Thermal and Photochemical Pathways

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