DFT/BP86/TZVP and DFT/B3LYP/TZVP have been used to investigate systematically the reaction pathways associated with the H-transfer step, which is the rate-determining step of the reaction HCOO- reversible arrow CO2 + H+ + 2e(-), as catalyzed by metalloenzyme formate dehydrogenase (FDH). Actually, the energetics associated with the transfer from formate to all H (proton or hydride) acceptors that are present within the FDH active site have been sampled. This study points to a viable intimate mechanism in which the metal center mediates H transfer from formate to the final acceptor, i.e. a selenocysteine residue. The Mo-based reaction pathway, consisting of a beta-H elimination to metal with concerted decarboxylation, turned out to be favored over previously proposed routes in which proton transfer occurs directly from HCOO- to selenocysteine. The proposed reaction pathway is reminiscent of the key step of metal-based catalysis of the water-gas shift reaction.

Tiberti, M., Papaleo, E., Russo, N., DE GIOIA, L., Zampella, G. (2012). Evidence for the Formation of a Mo-H Intermediate in the Catalytic Cycle of Formate Dehydrogenase. INORGANIC CHEMISTRY, 51(15), 8331-8339 [10.1021/ic300863d].

Evidence for the Formation of a Mo-H Intermediate in the Catalytic Cycle of Formate Dehydrogenase

DE GIOIA, LUCA;ZAMPELLA, GIUSEPPE
2012

Abstract

DFT/BP86/TZVP and DFT/B3LYP/TZVP have been used to investigate systematically the reaction pathways associated with the H-transfer step, which is the rate-determining step of the reaction HCOO- reversible arrow CO2 + H+ + 2e(-), as catalyzed by metalloenzyme formate dehydrogenase (FDH). Actually, the energetics associated with the transfer from formate to all H (proton or hydride) acceptors that are present within the FDH active site have been sampled. This study points to a viable intimate mechanism in which the metal center mediates H transfer from formate to the final acceptor, i.e. a selenocysteine residue. The Mo-based reaction pathway, consisting of a beta-H elimination to metal with concerted decarboxylation, turned out to be favored over previously proposed routes in which proton transfer occurs directly from HCOO- to selenocysteine. The proposed reaction pathway is reminiscent of the key step of metal-based catalysis of the water-gas shift reaction.
Articolo in rivista - Articolo scientifico
DENSITY-FUNCTIONAL THERMOCHEMISTRY; X-RAY CRYSTAL-STRUCTURE; CARBON-DIOXIDE; CORRELATION-ENERGY; REACTION-MECHANISM; ESCHERICHIA-COLI; MOLYBDOPTERIN; COMPLEXES
English
2012
51
15
8331
8339
none
Tiberti, M., Papaleo, E., Russo, N., DE GIOIA, L., Zampella, G. (2012). Evidence for the Formation of a Mo-H Intermediate in the Catalytic Cycle of Formate Dehydrogenase. INORGANIC CHEMISTRY, 51(15), 8331-8339 [10.1021/ic300863d].
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/10281/37186
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