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投稿者: Yuma Morimoto

Communication

Oxidation of Water by a Nonheme Diiron(IV) Complex via Proton-Coupled Electron Transfer

Chem. Commun., 2013, Accepted Manuscript

DOI: 10.1039/C3CC46391E
Received 21 Aug 2013, Accepted 25 Sep 2013
First published online 26 Sep 2013
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Yuma Morimoto さんの投稿…
1.ルテニウム五価オキソを用いた水の酸化反応ではO–Oボンドフォーメーションが進行するのに対して、この二核鉄四価ミューオキソ錯体ではヒドロキシルラジカルが生成するのは、この鉄錯体の還元電位が、H2Oを一電子酸化し、HO•を生成できるほどに高いことと、Fe(IV)Fe(IV)/Fe(III)Fe(IV)とFe(III)Fe(IV)/Fe(III)Fe(III)の差が、Ru(V)/Ru(IV)とRu(IV)/Ru(III)の差より大きいため、単核ルテニウムの系と比べて一電子プロセスが進行しやすいと説明している。
2.OH結合切断について。tBuOHの酸化の場合と異なり、H2O濃度に二次の依存性を示している事について、水がBaseとして働く、Termolecure Reactionが律速と説明。アイリングプロットを取って、その活性化エネルギーを比較しているが、反応次数の異なる二つの反応の活性化エネルギーをどのように比べているのか説明がほしい。
3.個人的に、水の一電子酸化電位2.13 V vs NHE in MeCN, 2.31 V in H2O (pH = 7.0)についてのRefは収穫。D. T. Sawyer, A. Sobkowiak and J. L. Roberts, Jr., in
Electrochemistry for Chemists, eds. D. T. Sawyer, A. Sobkowiak and J. L. Roberts, Jr., John Wiley & Sons, Inc., New York, 1995, Ch. 9, p. 358.
2013年9月30日 18:56
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