The reactions of LCuCl (L = 2,4-bis((2,6-diisopropylphenyl)imido)pentane (L(iPr)), 2,4-bis((2,6-diisopropylphenyl)imido)-3-chloropentane (L(CliPr))) with the phenolates TlOAr (Ar = C(6)H(3)Me(2), C(6)H(4)OMe, C(6)H(4)tBu) and NaOC(6)H(3)(tBu)(2) were explored. Novel three-coordinate Cu(II)-phenolates, LCuOAr, were isolated from the reactions with the thallium phenolates and were characterized by X-ray crystallography and spectroscopy (UV-vis, EPR). The complexes feature short Cu-O(phenolate) distances (average Cu-O = 1.81 A) and, with one exception, irregular N-Cu-O(phenolate) angles that differ within each compound (15 degrees < Delta < 28 degrees, where Delta = angleN(1)-Cu-O - angleN(2)-Cu-O). The exception is L(iPr)Cu(OC(6)H(4)tBu), for which X-ray structures at -100 and 25 degrees C differed due to an unusual reversible phase change with nonmerohedral twinning (2:1 ratio) in the low-temperature form. The high-temperature form has local C(2)(v) symmetry (Delta = 0 degrees ), and upon cooling below the phase transition temperature (-8 +/- 5 degrees C) lateral movement of the phenolate ligand (Delta = 17.6 degrees ) and rotation of the phenolate plane by 10.7 degrees occurs. Resonance Raman spectroscopic data acquired for L(iPr)Cu(OC(6)H(4)tBu) corroborated assignment of phenolate --> Cu(II) LMCT character in the UV-vis spectra. Cyclic voltammetry experiments (THF, 0.5 M NBu(4)PF(6)) revealed negative E(1/2) values for the Cu(II)/Cu(I) couples relative to NHE, consistent with enhanced stabilization of the Cu(II) state by both the strongly electron donating beta-diketiminate ligand and the phenolates. Although thermally stable, the Cu(II)-phenolates are unusually reactive with dioxygen, albeit to give product(s) that have yet to be identified. In the reaction of L(iPr)CuCl with NaOC(6)H(3)(tBu)(2) no Cu(II)-phenolate was observed. Instead, a Cu(I) complex was generated quantitatively by trapping with added isocyanide, [L(iPr)CuNC(C(6)H(3)Me(2))], along with 3,3',5,5'-tetra-tert-butyl-4,4'-dibenzoquinone and 2,6-di-tert-butylphenol in 27 +/- 3% and 46 +/- 6% yields, respectively, corresponding to the overall reaction 4L(iPr)Cu(II)Cl + 4NaOAr --> 4L(iPr)Cu(I) + 4NaCl + dibenzoquinone + 2(phenol).