We report the enhanced reactivity of hydroxyl substituted CuN3+ derivatives, where N-3 = tris(picolinyl)methane (tripic) and related derivatives, upon deprotonation of the O-H functionality. The work capitalizes on new methodology for incorporating hydroxyl groups into the second coordination sphere of copper centers. The key synthetic methodology relies on Pd-catalyzed coupling reactions of dilithiated 6-methyl-2-pyridone with bromopyridyl derivatives. These building blocks allow the preparation of tridentate N-3 ligands with OH and OMe substituents flanking the fourth coordination site of a tetrahedral complex. Coupling of these tridendate ligands gives the corresponding hydroxy- and methoxy-functionalized bistripodal ligands. [Cu[bis(2-methylpyrid-6-yl)(2-hydroxypyrid-6-yl)methane(NCMe)](+) ([Cu(2H)(NCMe)](+)) oxidizes readily in air to afford the mixed valence Cu-1.5 dimer ([Cu-2(2)(2)](+)). Formation of [Cu-2(2)(2)](+) is accelerated in the presence of base and can be reversed with a combination of decamethylferrocene and acid. The reactivity of [Cu(2H)(NCMe)](+) with dioxygen requires deprotonation of the hydroxyl substituent: neither [Cu(tripic)(NCMe)](+) nor the methoxy-derivatives displayed comparable reactivity. A related mixed valence dimer formed upon oxidation of the dicopper(I) complex of a tetrahydroxy bis(tridentate) ligand, [Cu-2(6H(4))(NCMe)(2)](2+). The dicopper(I) complex of the analogous tetramethoxy N-6-ligand, [Cu-2(5)(NCMe)(2)](2+), instead reversibly binds O-2. Deprotonation of [Cu(2H)(CO)](+) and [Cu(2H)(NCMe)](+) afforded the neutral derivatives Cu(2)(CO) and Cu-2(2)(2), respectively. The dicopper(I) derivative Cu-2(2)(2) can be reoxidized, reprotonated, and carbonylated. The silver(I) complex, [Ag(2H)(NCMe)]BF4, forms an analogous neutral dimer (Ag-2(2)(2)) upon deprotonation of the hydroxyl group. The structures of ligand 2H, [Cu-2(5)(NCMe)(2)](+), [Cu-2(2)(2)](+), [Cu-2(6H(2))](+), [Ag(2H)(NCMe)]BF4, and Ag-2(2)(2) were confirmed by single crystal X-ray diffraction.