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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

金属离子对非血红素高价锰氧配合物反应活性的影响

基本信息

批准号：
14J00541
负责人：
尹熙晶
金额：
$ 1.41万
依托单位：
Osaka University
依托单位国家：
日本
项目类别：
Grant-in-Aid for JSPS Fellows
财政年份：
2014
资助国家：
日本
起止时间：
2014-04-25 至 2016-03-31
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-14J00541/
关键词：
electron transfer oxygen atom transfer metal-oxygen species nonheme metal oxo electrochemistry redox-inactive metal ion manganese Metal-Oxo Complexes Enzyme Model Lewis Acid Effect Hydride Transfer Electron Transfer

项目摘要

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.

通过调节仿生反应中金属-氧中间体的化学性质，研究了氧化还原惰性金属离子对反应速率的扩展影响。水分子对非血红素铁（III）-过氧络合物结合氧化还原惰性金属离子的氧化还原性质的影响已发表在2015年的《化学》欧洲杂志上。在（TMC）Fe Ⅲ-（O2）-Zn ~（2+）体系中，两个水分子与一个Zn ~（2+）离子配位，降低了Zn ~（2+）离子的刘易斯酸性，从而提高了体系的单电子还原电位。另一部分是质子（HOTf）在[（Bn-TPEN）MnIV（O）-（HOTf）2]2+到PPh 3衍生物的氧原子转移中的作用。研究了膦衍生物的氧化反应，特别是质子（HOTf）的影响。它是通过直接的氧原子转移而不是电子转移进行的，尽管电子转移是放能的，与相应的氧原子转移到硫代苯甲醚衍生物形成鲜明对比。当电子转移的重组能与双电子过程的重组能竞争时，电子过程如直接氧原子转移。