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
收藏
页码：17572 / 17576
页数：5
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