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). 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.