Impact of Intramolecular Hydrogen Bonding on the Reactivity of Cupric Superoxide Complexes with O-H and C-H Substrates

被引：42

作者：

Diaz, Daniel E. ^{[1
]}

Quist, David A. ^{[1
]}

Herzog, Austin E. ^{[1
]}

Schaefer, Andrew W. ^{[2
]}

Kipouros, Ioannis ^{[2
]}

Bhadra, Mayukh ^{[1
]}

Solomon, Edward, I ^{[2
]}

Karlin, Kenneth D. ^{[1
]}

机构：

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

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

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2019年 / 58卷 / 49期

基金：

美国国家卫生研究院;

关键词：

copper monooxygenases; cupric superoxide; dioxygen reduction; H-atom transfer; hydrogen bonding; COPPER-COMPLEXES; OXYGEN; ACTIVATION; OXIDATION; DIOXYGEN; HYDROXYLATION; SPECTROSCOPY; REDUCTION; INSIGHTS; ENZYME;

D O I：

10.1002/anie.201908471

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The dioxygen reactivity of a series of TMPA-based copper(I) complexes (TMPA=tris(2-pyridylmethyl)amine), with and without secondary-coordination-sphere hydrogen-bonding moieties, was studied at -135 degrees C in 2-methyltetrahydrofuran (MeTHF). Kinetic stabilization of the H-bonded [((X1)(X2) TMPA)Cu-II(O-2(.-))](+) cupric superoxide species was achieved, and they were characterized by resonance Raman (rR) spectroscopy. The structures and physical properties of [((X1)(X2) TMPA)Cu-II(N-3(-))](+) azido analogues were compared, and the O-2(.-) reactivity of ligand-Cu-I complexes when an H-bonding moiety is replaced by a methyl group was contrasted. A drastic enhancement in the reactivity of the cupric superoxide towards phenolic substrates as well as oxidation of substrates possessing moderate C-H bond-dissociation energies is observed, correlating with the number and strength of the H-bonding groups.

引用

页码：17572 / 17576

页数：5

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