REDOX CHEMISTRY OF IRON PICOLINATE COMPLEXES AND OF THEIR HYDROGEN-PEROXIDE AND DIOXYGEN ADDUCTS

被引：21

作者：

COFRE, P ^{[1
]}

RICHERT, SA ^{[1
]}

SOBKOWIAK, A ^{[1
]}

SAWYER, DT ^{[1
]}

机构：

[1] TEXAS A&M UNIV SYST,DEPT CHEM,COLLEGE STN,TX 77843

来源：

INORGANIC CHEMISTRY | 1990年 / 29卷 / 14期

关键词：

D O I：

10.1021/ic00339a022

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

In aprotic solvents the bis(picolinato)iron(II) [Fe(PA)2] and (2,6-pyridinedicarboxylato)iron(II) [Fe(DPA)] complexes react with hydrogen peroxide and with dioxygen to form a series of monooxygen and dioxygen intermediates and adducts [(PA)2FeOFe(PA)2 (1), (PA)2Fe(OO), (PA)2FeOFe(PA)2-HOOH (2), and their analogues with Fe(DPA)]. The electron-transfer chemistries of the complexes and of their oxygenated products have been characterized by cyclic voltammetry, controlled-potential electrolysis, and rotated ring-disk voltammetry. These results in combination with UV-visible spectrophotometric and magnetic measurements have been used to develop a self-consistent mechanism for the formation of (PA)2FeO(OO)Fe(PA)2 (3) from (PA)2FeOFe(PA)2(1) and HOOH and for its transformation of methylene carbons to ketones. In dimethylformamide, species 3 (formed from 1 and HOOH) spontaneously decomposes to singlet dioxygen (lO2) and 1. © 1990, American Chemical Society. All rights reserved.

引用

页码：2645 / 2651

页数：7

共 18 条

[1] THE REACTION OF SUPEROXIDE RADICALS WITH METAL PICOLINATE COMPLEXES [J].