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Grills DC, Farrington JA, Layne BH, et al. Mechanism of the formation of a Mn-based CO2 reduction catalyst revealed by pulse radiolysis with time-resolved infrared detection. J Am Chem Soc. 2014;136(15):5563-6doi: 10.1021/ja501051s.
Grills, D. C., Farrington, J. A., Layne, B. H., Lymar, S. V., Mello, B. A., Preses, J. M., & Wishart, J. F. (2014). Mechanism of the formation of a Mn-based CO2 reduction catalyst revealed by pulse radiolysis with time-resolved infrared detection. Journal of the American Chemical Society, 136(15), 5563-6. https://doi.org/10.1021/ja501051s
Grills, David C, et al. "Mechanism of the formation of a Mn-based CO2 reduction catalyst revealed by pulse radiolysis with time-resolved infrared detection." Journal of the American Chemical Society vol. 136,15 (2014): 5563-6. doi: https://doi.org/10.1021/ja501051s
Grills DC, Farrington JA, Layne BH, Lymar SV, Mello BA, Preses JM, Wishart JF. Mechanism of the formation of a Mn-based CO2 reduction catalyst revealed by pulse radiolysis with time-resolved infrared detection. J Am Chem Soc. 2014 Apr 16;136(15):5563-6. doi: 10.1021/ja501051s. Epub 2014 Apr 07. PMID: 24679111.
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J Am Chem Soc. 2014 Apr 16;136(15):5563-6. doi: 10.1021/ja501051s. Epub 2014 Apr 07.

Mechanism of the formation of a Mn-based CO2 reduction catalyst revealed by pulse radiolysis with time-resolved infrared detection.

Journal of the American Chemical Society

David C Grills, Jaime A Farrington, Bobby H Layne, Sergei V Lymar, Barbara A Mello, Jack M Preses, James F Wishart

Affiliations

  1. Chemistry Department, Brookhaven National Laboratory, P.O. Box 5000, Upton, New York 11973-5000, United States.

PMID: 24679111 DOI: 10.1021/ja501051s

Abstract

Using a new technique, which combines pulse radiolysis with nanosecond time-resolved infrared (TRIR) spectroscopy in the condensed phase, we have conducted a detailed kinetic and mechanistic investigation of the formation of a Mn-based CO2 reduction electrocatalyst, [Mn((t)Bu2-bpy)(CO)3]2 ((t)Bu2-bpy = 4,4'-(t)Bu2-2,2'-bipyridine), in acetonitrile. The use of TRIR allowed, for the first time, direct observation of all the intermediates involved in this process. Addition of excess [(n)Bu4N][HCO2] to an acetonitrile solution of fac-MnBr((t)Bu2-bpy)(CO)3 results in its quantitative conversion to the Mn-formate complex, fac-Mn(OCHO)((t)Bu2-bpy)(CO)3, which is a precatalyst for the electrocatalytic reduction of CO2. Formation of the catalyst is initiated by one-electron reduction of the Mn-formate precatalyst, which produces the bpy ligand-based radical. This radical undergoes extremely rapid (τ = 77 ns) formate dissociation accompanied by a free valence shift to yield the five-coordinate Mn-based radical, Mn(•)((t)Bu2-bpy)(CO)3. TRIR data also provide evidence that the Mn-centered radical does not bind acetonitrile prior to its dimerization. This reaction occurs with a characteristically high radical-radical recombination rate (2kdim = (1.3 ± 0.1) × 10(9) M(-1) s(-1)), generating the catalytically active Mn-Mn bound dimer.

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