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由α,α'-二甲基-2,11-二氮杂[3,3](2,6)吡啶并环催化的水氧化反应。铁氧中间体的光谱学及密度泛函理论计算。

Water oxidation catalysed by iron complex of ,'-dimethyl-2,11-diaza[3,3](2,6)pyridinophane. Spectroscopy of iron-oxo intermediates and density functional theory calculations.

作者信息

To Wai-Pong, Wai-Shan Chow Toby, Tse Chun-Wai, Guan Xiangguo, Huang Jie-Sheng, Che Chi-Ming

机构信息

Department of Chemistry and State Key Laboratory of Synthetic Chemistry , The University of Hong Kong , Pokfulam Road , Hong Kong , China . Email:

HKU Shenzhen Institute of Research and Innovation , Shenzhen 518053 , China.

出版信息

Chem Sci. 2015 Oct 1;6(10):5891-5903. doi: 10.1039/c5sc01680k. Epub 2015 Jul 22.

DOI:10.1039/c5sc01680k
PMID:29861914
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC5950833/
Abstract

The macrocyclic [Fe(L1)Cl] (, L1 = ,'-dimethyl-2,11-diaza3,3pyridinophane) complex is an active catalyst for the oxidation of water to oxygen using [NH][Ce(NO)] (CAN), NaIO, or Oxone as the oxidant. The mechanism of -catalysed water oxidation was examined by spectroscopic methods and by O-labelling experiments, revealing that Fe[double bond, length as m-dash]O and/or Fe[double bond, length as m-dash]O species are likely to be involved in the reaction. The redox behaviour of and these high-valent Fe[double bond, length as m-dash]O species of L1 has been examined by both cyclic voltammetry and density functional theory (DFT) calculations. In aqueous solutions, the cyclic voltammograms of at different pH show a pH-dependent reversible couple ( = +0.46 V SCE at pH 1) and an irreversible anodic wave ( = +1.18 V SCE at pH 1) assigned to the Fe/Fe couple and the Fe to Fe oxidation, respectively. DFT calculations showed that the value of the half reaction involving [Fe(L1)(O)(OH)]/[Fe(L1)(O)(OH)] is +1.42 V SCE at pH 1. Using CAN as the oxidant at pH 1, the formation of an Fe[double bond, length as m-dash]O reaction intermediate was suggested by ESI-MS and UV-vis absorption spectroscopic measurements, and the rate of oxygen evolution was linearly dependent on the concentrations of both and CAN. Using NaIO or Oxone as the oxidant at pH 1, the rate of oxygen evolution was linearly dependent on the concentration of , and a reactive Fe[double bond, length as m-dash]O species with formula [Fe(L1)(O)] generated by oxidation with NaIO or Oxone was suggested by ESI-MS measurements. DFT calculations revealed that [Fe(L1)(O)] is capable of oxidizing water to oxygen with a reaction barrier of 15.7 kcal mol.

摘要

大环化合物[Fe(L1)Cl]（L1 = ，'-二甲基-2,11-二氮杂3,3吡啶并环）配合物是以[NH][Ce(NO)]（CAN）、NaIO或过一硫酸氢钾复合盐作为氧化剂将水氧化为氧气的活性催化剂。通过光谱方法和O标记实验研究了 -催化水氧化的机理，结果表明Fe=O和/或Fe=O物种可能参与了该反应。通过循环伏安法和密度泛函理论（DFT）计算研究了 和L1的这些高价Fe=O物种的氧化还原行为。在水溶液中， 在不同pH值下的循环伏安图显示出一个pH依赖的可逆偶合（pH = 1时 = +0.46 V SCE）和一个不可逆阳极波（pH = 1时 = +1.18 V SCE），分别归属于Fe/Fe偶合和Fe到Fe的氧化。DFT计算表明，在pH = 1时，涉及[Fe(L1)(O)(OH)]/[Fe(L1)(O)(OH)]的半反应的值为+1.42 V SCE。在pH = 1时以CAN作为氧化剂，通过电喷雾电离质谱（ESI-MS）和紫外可见吸收光谱测量表明形成了Fe=O反应中间体，并且析氧速率与 和CAN的浓度呈线性相关。在pH = 1时以NaIO或过一硫酸氢钾复合盐作为氧化剂，析氧速率与 的浓度呈线性相关，并且ESI-MS测量表明通过用NaIO或过一硫酸氢钾复合盐氧化生成了化学式为[Fe(L1)(O)]的活性Fe=O物种。DFT计算表明，[Fe(L1)(O)]能够将水氧化为氧气，反应势垒为15.7 kcal mol。

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