Oxyl radical required for O-O bond formation in synthetic Mn-catalyst

被引：118

作者：

Lundberg, M ^{[1
]}

Blomberg, MRA ^{[1
]}

Siegbahn, PEM ^{[1
]}

机构：

[1] Univ Stockholm, Dept Phys, AlbaNova Univ Ctr, Stockholm Ctr Phys Astrom & Biotechnol, SE-10691 Stockholm, Sweden

来源：

INORGANIC CHEMISTRY | 2004年 / 43卷 / 01期

关键词：

D O I：

10.1021/ic0348188

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

DFT calculations using the B3LYP functional support the suggestion that the [(terpy)(H2O)Mn-IV(mu-O)(2)Mn-III(H2O)-(terpy)](3+) (terpy=2,2':6,2"-terpyridine) complex functions as a synthetic O-2 catalyst. The calculated barrier for O-O bond formation with water is 23 kcal/mol. In this complex, as well as in models of the oxygen evolving complex in PSII, the active species is a Mn-IV-oxyl radical. From comparisons with inactive Mn-V-oxo complexes, it is proposed that radical formation is actually a requirement for O-2 formation activity in Mn-complexes.

引用

页码：264 / 274

页数：11

共 30 条

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