Research Project
Grant-in-Aid for JSPS Fellows
The extended effect of redox-inactive metal ions on the reaction rates has been studied by tuning the chemical properties of metal-oxygen intermediates in biomimetic reactions. The effect of water molecules on the redox properties of nonheme iron(III)-peroxo complexes binding redox-inactive metal ions has been published in Chemistry a European Journal 2015. The coordination of two water molecules to a Zn2+ ion in (TMC)FeIII-(O2)-Zn2+ decreases the Lewis acidity of Zn2+ ion, resulting in the increase in the one-electron reduction potentials of (TMC)FeIII-(O2)-Zn2+. The other part was the effect of proton (HOTf) in oxygen atom transfer from [(Bn-TPEN)MnIV(O)－(HOTf)2]2+ to PPh3 derivatives. The oxidation reaction of phosphine derivatives has been examined especially with regard to the effects of proton (HOTf). It proceeds via direct oxygen atom transfer rather than electron transfer even though the electron transfer is exergonic in sharp contrast to the corresponding oxygen atom transfer to thioanisole derivatives.We have interpreted these results for the first time that the rate of exergonic electron transfer can be slower than that of the two-electron process such as direct oxygen atom transfer when the reorganization energy of electron transfer is to compete with that of the two-electron process.
27年度が最終年度であるため、記入しない。
All 2015 2014 Other
All Int'l Joint Research (1 results) Journal Article (3 results) (of which Int'l Joint Research: 1 results, Peer Reviewed: 3 results, Open Access: 2 results, Acknowledgement Compliant: 3 results) Presentation (2 results)
Chemical Science
Volume: no page Issue: 6 Pages: 3624-3632
10.1039/c5sc00535c
Chem. Eur. J.
Volume: 21 Issue: 30 Pages: 10676-10680
10.1002/chem.201502143
Chemical Communications
Volume: 50 Issue: 85 Pages: 12944-12946
10.1039/c4cc05313c
