Thermodynamics of a μ-oxo Dicopper(II) Complex for Hydrogen Atom Abstraction

被引：31

作者：

Ali, Ghazanfar ^{[1
]}

VanNatta, Peter E. ^{[1
]}

Ramirez, David A. ^{[1
]}

Light, Kenneth M. ^{[1
]}

Kieber-Emmons, Matthew T. ^{[1
]}

机构：

[1] Univ Utah, Dept Chem, Salt Lake City, UT 84112 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2017年 / 139卷 / 51期

基金：

美国国家科学基金会;

关键词：

PARTICULATE METHANE MONOOXYGENASE; ACTIVE-SITE; OXIDATION; OXYGEN; CONVERSION; ZEOLITES; CU-ZSM-5; BINDING;

D O I：

10.1021/jacs.7b10833

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The mono-mu-hydroxo complex {[Cu-(tmpa)](2)-(mu-OH)}(3+) (1) can undergo reversible deprotonation at -30 degrees C to yield {[Cu(tmpa)](2)-(mu-O)}(2+) (2). This species is basic with a pK(a) of 24.3. 2 is competent for concerted proton-electron transfer from TEMPOH, but is an intrinsically poor hydrogen atom abstractor (BDFE-(OH) of 77.2 kcal/mol) based on kinetic and thermodynamic analyses. Nonetheless, DFT calculations experimentally calibrated against 2 reveal that [Cu2O](2+) is likely thermodynamically viable in copper-dependent methane monoxygenase enzymes.

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收藏

页码：18448 / 18451

页数：4

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