Mechanistic insights into CO2 conversion to CO using cyano manganese complexes

Kailyn Y. Cohen, Delaan G. Nedd, Rebecca Evans, Andrew B. Bocarsly

Research output: Contribution to journalArticlepeer-review

3 Scopus citations

Abstract

Without the use of a photosensitizer, [Mn(bpy)(CO)3(CN)] (MnCN) can photochemically form [Mn(bpy)(CO)3], the active species for CO2 reduction. While cases of the axial X-ligand dissociating upon irradiation of fac-[M(N-N)(CO)3X] complexes (M = Mn or Re; N-N = bipyridine (bpy) ligand; X = halogen or pseudohalogen) are well documented, the axial cyanide ligand is retained when either [Mn(bpy)(CO)3(CN)] or [Mn(mesbpy)(CO)3(CN)], MnCN(mesbpy), are irradiated anaerobically. Infrared and UV-vis spectroscopies indicate the formation of [Mn(bpy)(CO)2(MeCN)(CN)] (s-MnCN) as the primary product during the irradiation of MnCN. An in-depth analysis of the photochemical mechanism for the formation of [Mn(bpy)(CO)3] from MnCN is presented. MnCN(mesbpy) is too sterically hindered to undergo the same photochemical mechanism as MnCN. However, MnCN(mesbpy) is found to be electrocatalytically active for CO2 reduction to CO. Thus providing an interesting distinction between photochemical and electrochemical charge transfer.

Original languageEnglish (US)
Pages (from-to)7524-7537
Number of pages14
JournalDalton Transactions
Volume52
Issue number22
DOIs
StatePublished - May 15 2023

All Science Journal Classification (ASJC) codes

  • Inorganic Chemistry

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