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
A high-potential nonhaem (μ-oxo)diiron(IV) complex was found to oxidize water to hydroxyl radical via PCET, instead of forming an O–O bond. The rate-determining step requires a second water molecule, proposed to act as a base to promote proton transfer. This work shows that additional factors besides a high redox potential are required to effect O–O bond formation.
コメント
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.