COPPER DIOXYGEN CHEMISTRY AND MODELING THE FE-CU CENTER IN CYTOCHROME-C-OXIDASE

被引：26

作者：

KARLIN, KD

FOX, S

NANTHAKUMAR, A

MURTHY, NN

WEI, N

OBIAS, HV

MARTENS, CF

机构：

[1] Department of Chemistry, The Johns Hopkins University, Baltimore, Maryland 21218

来源：

PURE AND APPLIED CHEMISTRY | 1995年 / 67卷 / 02期

关键词：

D O I：

10.1351/pac199567020289

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The copper(I) complex [(TMPA)Cu(RCN)]+ (1) binds O2 forming [{(TMPA)Cu}2-(O2)]2+ (2), with trans-mu-1, 2 peroxo-coordination. Ligands with quinolyl groups substituting for the pyridyl donors in TMPA cause dramatic changes in the course of reaction, in one case stabilizing a Cu/O2 1:1 adduct [BQPA)Cu(O2)]+ (6). The kinetics/thermodynamics are compared. Reaction of 1 with (F8-TPP)Fe(II)pip2 (8) and O2 yields the mu-oxo species [F8-TPP)Fe(III)-O-Cu(II)(TMPA)]+ (9); this reversibly protonates giving mu-hydroxo bridged [(F8-TPP)Fe-(OH)-Cu(TMPA)]2+ (12). The novel NMR properties of 9 are described. These complexes are discussed in terms of their model O2-chemistry in hemocyanins or cytochrome c oxidase.

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页码：289 / 296

页数：8

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