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

Journal Article · · ACS Catalysis
 [1];  [2];  [2];  [2];  [2];  [2]
  1. Princeton Univ., NJ (United States); Princeton University
  2. Princeton Univ., NJ (United States)
+ Show Author Affiliations
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.
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, Journal Name: 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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Related Subjects

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