Direct Observation by Rapid-Scan FT-IR Spectroscopy of Two-Electron-Reduced Intermediate of Tetraaza Catalyst [CoIIN4H(MeCN)]2+ Converting CO 2 to CO

Sheng, Hua; Frei, Heinz

doi:10.1021/jacs.6b05248

Direct Observation by Rapid-Scan FT-IR Spectroscopy of Two-Electron-Reduced Intermediate of Tetraaza Catalyst [Co^IIN₄H(MeCN)]²⁺ Converting CO ₂ to CO

Journal Article · Fri Jul 15 00:00:00 EDT 2016 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.6b05248· OSTI ID:1378345

Sheng, Hua ^[1]; Frei, Heinz ^[1]

Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Biophysics and integrated Bioimaging Division

In the search for the two-electron-reduced intermediate of the tetraaza catalyst [Co^IIN₄H(MeCN)]²⁺ (N₄H = 2,12-dimethyl-3,7,11,17-tetraazabicyclo[11.3.1]heptadeca-1(17),2,11,13,15-pentaene) for CO₂ reduction and elementary steps that result in the formation of CO product, rapid-scan FT-IR spectroscopy of the visible-light-sensitized catalysis, using Ir(ppy)₃ in wet acetonitrile (CD₃CN) solution, led to the observation of two sequential intermediates. The initially formed one-electron-reduced [Co^IN₄H]⁺--CO₂ adduct was converted by the second electron to a transient [Co^IN₄H]⁺--CO₂ - complex that spontaneously converted CO₂ to CO in a rate-limiting step on the second time scale in the dark under regeneration of the catalyst (room temperature). The macrocycle IR spectra of the [Co^IN₄H]⁺--CO₂ - complex and the preceding one-electron [Co^IN₄H]⁺--CO₂ intermediate show close similarity but distinct differences in the carboxylate modes, indicating that the second electron resides mainly on the CO₂ ligand. Vibrational assignments are corroborated by ¹³C isotopic labeling. The structure and stability of the two-electron-reduced intermediate derived from the time-resolved IR study are in good agreement with recent predictions by DFT electronic structure calculations. This is the first observation of an intermediate of a molecular catalyst for CO₂ reduction during the bond-breaking step producing CO. The reaction pathway for the Co tetraaza catalyst uncovered here suggests that the competition between CO₂ reduction and proton reduction of a macrocyclic multi-electron catalyst is steered toward CO₂ activation if the second electron is directly captured by an adduct of CO₂ and the one-electron-reduced catalyst intermediate.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

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

Grant/Contract Number:: AC02-05CH11231; SC0004993

OSTI ID:: 1378345

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 31 Vol. 138; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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