2014 Fiscal Year Annual Research Report
非ヘム高原子価マンガンオキソ錯体の反応性に及ぼす金属イオンの効果
| Project/Area Number |
14J00541
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| Research Institution | Osaka University |
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Principal Investigator |
尹 熙晶 大阪大学, 工学研究科, 特別研究員(DC2)
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| Project Period (FY) |
2014-04-25 – 2016-03-31
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| Keywords | Metal-Oxo Complexes / Enzyme Model / Lewis Acid Effect / Hydride Transfer / Electron Transfer |
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| Outline of Annual Research Achievements |
During 2014 research, extended work of Mn(IV)-oxo complexes has been mainly focused. The published result is ‘the mechanism of hydride transfer from NADH analogues to an nonheme Mn(IV)-oxo complex’ on Chemical Communication in 2014. Mn(IV)-oxo complex is compared with that of hydride transfer to an Fe(IV)-oxo complex revealing the reaction proceeds via a rate-determining electron transfer with no deuterium kinetic isotope effect. Therefore, a charge-transfer complex formed between the Mn(IV)-oxo complex and NADH analogues is clarified in the hydride transfer reaction. Also, The factors that tune the redox reactivity of the oxo intermediates were thoroughly investigated especially with the effects of proton. Diprotonated nonheme Mn(IV)-oxo complexes, [(L)MnIV(O)]2+－(HOTf)2, were synthesized by adding HOTf and were characterized by various spectroscopic methods. The fundamental electron-transfer properties of [(L)MnIV(O)]2+－(HOTf)2 have also been investigated to compare the reactivities with OAT and HAT reactions.
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| Current Status of Research Progress |
Current Status of Research Progress
2: Research has progressed on the whole more than it was originally planned.
Reason
I have been carrying on multiple projects, of course, some of them resulted with published papers and some of them is not. First of all, I have successfully summarized my work on Hydride Transfer by Manganese(IV)-oxo complexes and it appeared on RSC Chemical Communications. In addition, Proton effect on Manganese(IV)-oxo complexes was a bit complicated, but recently it was accepted at RSC Chemical Science. I am proud of such a result for a year and hope that it will be continuously studied for next another year.
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| Strategy for Future Research Activity |
Currently i have on going research on Lewis acid effect on Manganese(IV)-oxo complexes combining with water effect for that matter. So far, interesting key data has been obtained and i am certain that it will be successfully finished. In addition, I have found very interesting data on photo-irradiated metal complexes. It seems challenging but i am happy to be the pioneer of researching of very undiscovered area.
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