"Criss-Crossed" Dinucleating Behavior of an N4 Schiff Base Ligand: Formation of a μ-OH,μ-O2 Dicobalt(III) Core via O2 Activation

被引：26

作者：

Cho, Yae In ^{[1
]}

Joseph, David M. ^{[1
]}

Rose, Michael J. ^{[1
]}

机构：

[1] Univ Texas Austin, Dept Chem, Austin, TX 78713 USA

来源：

INORGANIC CHEMISTRY | 2013年 / 52卷 / 23期

关键词：

DIOXYGEN REDUCTION; COBALT COMPLEXES; WATER OXIDATION; EPR; OXYGEN; CATALYST;

D O I：

10.1021/ic402391f

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

We report the synthesis and structural characterization of a dicobalt(III) complex with a mu-OH,mu-O-2 core, namely mu-OH,mu-O-2-[Co(enN4)](2)(X)(3) [1(ClO4)(3) and 1(BF4)(3)]. The dinuclear core is cross-linked by two N4 Schiff base ligands that span each cobalt center. The formally Co-III-Co-III dimer is formed spontaneously upon exposure of the mononuclear Co(II) complex to air and exhibits a nu(O-O) value at 882 cm(-1) that shifts to 833 cm(-1) upon substitution with O-18(2). The CV of 1(BF4)(3) exhibits a reversible {Co-III-Co-III}<->{Co-III-Co-IV} redox process, and we have investigated the oxidized {Co-III-Co-IV} species by EPR spectroscopy (g = 2.02, 2.06; S = 1/2 signal) and DFT calculations.

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页码：13298 / 13300

页数：3

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