电子可用性对合成单金属铁卟啉还原O2选择性的影响。

Effect of electron availability on selectivity of O2 reduction by synthetic monometallic Fe porphyrins.

作者信息

Collman James P, Shiryaeva Irina M, Boulatov Roman

机构信息

Department of Chemistry, Stanford University, Stanford, California 94305, USA.

出版信息

Inorg Chem. 2003 Aug 11;42(16):4807-9. doi: 10.1021/ic034488r.

DOI:10.1021/ic034488r

PMID:12895101

Abstract

Herein we report that biomimetic analogues of cytochrome c oxidase (CcO) couple reduction of O(2) to oxidation of a single-electron carrier, Ru(NH(3))(6)(2+), under steady-state catalytic turnover. Higher Ru(II) concentrations favor the 4-electron vs 2-electron O(2) reduction pathway. Our data indicate that the capacity of electrode-adsorbed Fe-only porphyrins to catalyze reduction of O(2) to H(2)O is due to high availability of electrons and is eliminated under the biologically relevant slow electron delivery.

摘要

在此我们报告，细胞色素c氧化酶（CcO）的仿生类似物在稳态催化周转下，能将O₂的还原与单电子载体Ru(NH₃)₆²⁺的氧化偶联起来。较高的Ru(II)浓度有利于4电子而非2电子的O₂还原途径。我们的数据表明，电极吸附的仅含铁卟啉催化O₂还原为H₂O的能力归因于电子的高可用性，并且在生物学相关的缓慢电子传递条件下这种能力会消失。