Intramolecular Hydrogen Bonding Enhances Stability and Reactivity of Mononuclear Cupric Superoxide Complexes

被引：77

作者：

Bhadra, Mayukh ^{[1
]}

Lee, Jung Yoon C. ^{[1
]}

Cowley, Ryan E. ^{[2
]}

Kim, Sunghee ^{[1
]}

Siegler, Maxime A. ^{[1
]}

Solomon, Edward, I ^{[2
]}

Karlin, Kenneth D. ^{[1
]}

机构：

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

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

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2018年 / 140卷 / 29期

关键词：

COPPER-DIOXYGEN ADDUCT; END-ON; SUBSTRATE HYDROXYLATION; GALACTOSE-OXIDASE; O-2; ACTIVATION; NITRIC-OXIDE; ACTIVE-SITE; OXYGEN; OXIDATION; LIGANDS;

D O I：

10.1021/jacs.8b04671

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

[(L)Cu-II(O-2(center dot-)](+) (i.e., cupric-superoxo) complexes, as the first and/or key reactive intermediates in (bio)chemical Cu-oxidative processes, including in the monooxygenases PHM and D beta M, have been systematically stabilized by intramolecular hydrogen bonding within a TMPA ligand-based framework. Also, gradual strengthening of ligand-derived H-bonding dramatically enhances the [(L)Cu-II(O-2(center dot-)](+) reactivity toward hydrogen-atom abstraction (HAA) of phenolic O-H bonds. Spectroscopic properties of the superoxo complexes and their azido analogues, [(L)Cu-II(N-3(-)](+), also systematically change as a function of ligand H-bonding capability.

引用

页码：9042 / 9045

页数：4

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