Thermodynamics of a μ-oxo Dicopper(II) Complex for Hydrogen Atom Abstraction
- PMID: 29207870
- DOI: 10.1021/jacs.7b10833
Thermodynamics of a μ-oxo Dicopper(II) Complex for Hydrogen Atom Abstraction
Abstract
The mono-μ-hydroxo complex {[Cu(tmpa)]2-(μ-OH)}3+ (1) can undergo reversible deprotonation at -30 °C to yield {[Cu(tmpa)]2-(μ-O)}2+ (2) VSports手机版. This species is basic with a pKa 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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