Correlation of the Electronic and Geometric Structures in Mononuclear Copper(II) Superoxide Complexes

被引：42

作者：

Ginsbach, Jake W. ^{[1
]}

Peterson, Ryan L. ^{[2
]}

Cowley, Ryan E. ^{[1
]}

Karlin, Kenneth D. ^{[2
]}

Solomon, Edward I. ^{[1
]}

机构：

[1] Stanford Univ, Dept Chem, Stanford, CA 94305 USA

[2] Johns Hopkins Univ, Dept Chem, Baltimore, MD 21218 USA

来源：

INORGANIC CHEMISTRY | 2013年 / 52卷 / 22期

关键词：

END-ON; DIOXYGEN ADDUCT; CU-II; MONOOXYGENASE; ACTIVATION;

D O I：

10.1021/ic402357u

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The geometry of mononuclear copper(II) superoxide complexes has been shown to determine their ground state where side-on bonding leads to a singlet ground state and end-on complexes have triplet ground states. In an apparent contrast to this trend, the recently synthesized (HIPT(3)tren)(CuO2 center dot-)-O-II (1) was proposed to have an end-on geometry and a singlet ground state. However, reexamination of 1 with resonance Raman, magnetic circular dichroism, and H-2 NMR spectroscopies indicate that 1 is, in fact, an end-on superoxide species with a triplet ground state that results from the single (CuO2 center dot-)-O-II bonding interaction being weaker than the spin-pairing energy.

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收藏

页码：12872 / 12874

页数：3

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