Unexpected Roles of Triethanolamine in the Photochemical Reduction of CO2 to Formate by Ruthenium Complexes

Sampaio, Renato N.; Grills, David C.; Polyansky, Dmitry E.; Szalda, David J.; Sampaio, Renato N.

doi:10.1021/jacs.9b11897

Unexpected Roles of Triethanolamine in the Photochemical Reduction of CO₂ to Formate by Ruthenium Complexes

Journal Article · Fri Dec 27 00:00:00 EST 2019 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.9b11897· OSTI ID:1595690

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Brookhaven National Lab. (BNL), Upton, NY (United States). Dept. of Chemistry
City Univ. of New York (CUNY), NY (United States). Baruch College. Dept. of Natural Science

We show a series of 4,4'-dimethyl-2,2'-bipyridyl ruthenium complexes with carbonyl ligands were prepared and studied using a combination of electrochemical and spectroscopic methods with infrared detection to provide structural information on reaction intermediates in the photochemical reduction of CO₂ to formate in acetonitrile (CH₃CN). An unsaturated 5-coordinate intermediate was characterized, and the hydride-transfer step to CO₂ from a singly reduced metal-hydride complex was observed with kinetic resolution. While triethanolamine (TEOA) was expected to act as a proton acceptor to ensure the sacrificial behavior of 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole as an electron donor, time-resolved infrared measurements revealed that about 90% of the photogenerated one-electron reduced complexes undergo unproductive back electron transfer. Furthermore, TEOA showed the ability to capture CO₂ from CH₃CN solutions to form a zwitterionic alkylcarbonate adduct and was actively engaged in key catalytic steps such as metal-hydride formation, hydride transfer to CO₂ to form the bound formate intermediate, and dissociation of formate ion product. Collectively, the data provide an overview of the transient intermediates of Ru(II) carbonyl complexes and emphasize the importance of considering the participation of TEOA when investigating and proposing catalytic pathways.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0012704

OSTI ID:: 1595690

Report Number(s):: BNL--213575-2020-JAAM

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 5 Vol. 142; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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CCDC 1980640: Experimental Crystal Structure Determination N., Sampaio, Renato; C., Grills, David; E., Polyansky, Dmitry https://doi.org/10.5517/ccdc.csd.cc24h0m9 The current record is supplemented by this dataset	dataset	January 2020
CCDC 1980641: Experimental Crystal Structure Determination N., Sampaio, Renato; C., Grills, David; E., Polyansky, Dmitry https://doi.org/10.5517/ccdc.csd.cc24h0nb The current record is supplemented by this dataset	dataset	January 2020