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• W2020166211 abstract "Nitrogenase enzymes containing molybdenum normally reduce N2 to NH3, and are severely inhibited by CO, but vanadium-nitrogenase reduces CO to hydrocarbons C2H4, C2H6 and C3H8. Aspects of the mechanism of this unexpected and unprecedented reaction have been investigated by density functional simulations of the iron-vanadium cofactor FeV-co [NFe7VS9(homocitrate)] protein-bound by cysteine and histidine. It is found that the intramolecular hydrogenating machinery previously proposed for N2reduction (including H-atom tunneling) can also effect reduction of CO. There are feasible steps for all of the requisite components of the overall reaction, namely (i) the binding of CO, (ii) the initial hydrogenation of CO to HCO, (iii) continued hydrogenations of CO at both C and O to HCOH and H2COH, (iv) eliminations of O as H2O, and (v) the C–C bond formation steps. Intermediate organic fragments can migrate around the active face of FeV-co, and hydrogen bonding between COH functions and S or SH components of FeV-co can occur and contribute to the stabilisation and orientation of intermediates. It is suggested that the difference between Mo-nitrogenase and V-nitrogenase occurs in the immediately surrounding protein, which facilitates (possibly viawater associated with homocitrate bound to V) the exogenous protonation and dehydration of –COH intermediates." @default.
• W2020166211 created "2016-06-24" @default.
• W2020166211 creator A5009429134 @default.
• W2020166211 date "2011-01-01" @default.
• W2020166211 modified "2023-09-23" @default.
• W2020166211 title "How does vanadium nitrogenase reduce CO to hydrocarbons?" @default.
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• W2020166211 doi "https://doi.org/10.1039/c1dt10240k" @default.
• W2020166211 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/21487574" @default.
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