The mono-μ-hydroxo complex {[Cu(tmpa)]-(μ-OH)} (1) can undergo reversible deprotonation at -30 °C to yield {[Cu(tmpa)]-(μ-O)} (2). This species is basic with a pK 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 [CuO] is likely thermodynamically viable in copper-dependent methane monoxygenase enzymes.
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