Facile Csp2–Csp2 Bond Cleavage in Oxalic Acid-Derived Radicals
作者： Robert W. Molt , Alison M. Lecher , Timothy Clark , Rodney J. Bartlett , Nigel G. J. Richards
DOI: 10.1021/JA510666R
关键词:
摘要: Oxalate decarboxylase (OxDC) catalyzes the Mn-dependent conversion of oxalate monoanion into CO2 and formate. Many questions remain about catalytic mechanism OxDC although it has been proposed that reaction proceeds via substrate-based radical intermediates. Using coupled cluster theory combined with implicit solvation models we have examined effects formation on structure reactivity oxalic acid-derived radicals in aqueous solution. Our results show calculated solution-phase free-energy barrier for C–C bond cleavage to form is decreased from 34.2 kcal/mol acid only 9.3 a maximum 3.5 cationic neutral radicals, respectively. These studies also σ bonding orbital cation contains single electron, giving rise an elongated distance 1.7 A; similar lengthening not observed radical. This study provides...
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