摘要 : We attempted to design Ru-aqua complexes that possess potential inversion behavior for sequential proton-coupled oxidation (PCO) reactions. Standard reduction potentials for [Ru~(III)(T)(B)(OH)]~(m+) + H~+ + e~- -> [Ru~(II)(T)(B)(... 展开 We attempted to design Ru-aqua complexes that possess potential inversion behavior for sequential proton-coupled oxidation (PCO) reactions. Standard reduction potentials for [Ru~(III)(T)(B)(OH)]~(m+) + H~+ + e~- -> [Ru~(II)(T)(B)(H2O)]~(m+) (F~ORu~(III/II))), [Ru~(IV)(T)(B)(O)]~(m+) + H~+ + e~- -> [Ru~(III)(T)(B)(OH)]~(m+) (P[Ru~(IV/III]) reactions as well as △E~° values (AE° = E°(Ru~(III/II)) - E°(Ru~(IV/III))) of newly designed 41 Ru-aqua complexes along with those of previously reported 13 known ones were calculated using the DFT method with PBE1PBE/def2SVP/SDD combination. Four complexes with negative AP values and nine complexes with AE° values smaller than 0.1 V were found by this screening work. The calculated AP values had a close relationship with E°(Ru~(III/II)). Complexes possessing large AP values showed relatively small E°(Ru~(III/II)) that gave rise to the increased gap with E°(Ru~(IV/III)). It was found that the distortion of electronic structures during progressing two PCO reactions is mostly responsible for the potential inversion. 收起