We have synthesized and characterized bis(mu-oxo)dicopper(lll) climers 1b-4b (Os) based on a core family of peralkylated trans-(1R,2R)-cyclohexanediamine (CD) ligands, self-assembled from the corresponding [LCu(MeCN)]CF(3)SO(3) species 1a-4a and O(2) at 193 K in aprotic media; additional Os based on peralkylated ethylenediamine and tridentate polyazacyclononane ligands were synthesized analogously for comparative purposes (5b-7b and 8b-9b, respectively). Trigonal-planar [LCu(MeCN)](1+) species are proposed as the active O precursors. The 3-coordinate Cu(l) complexes [(L(TE))CU(MeCN)]CF(3)SO(3) (4a) and [(L(TB))Cu(MeCN)]CF(3)SO(3) (10a) were structurally characterized; the apparent O(2)-inertness of 10a correlates with the steric demands of its four benzyl substituents. The rate of O formation, a multistep process that likely proceeds via associative formation of a 1:1 [LCu(O(2))](1+) intermediate, exhibits significant dependence upon ligand sterics and solvent: oxygenation of 4a-the slowest-reacting 0 precursor of the CD series-is first-order with respect to [4a] and proceeds at least 300 times faster in tetrahydrofuran than in CH(2)Cl(2). The EPR, UV-vis, and resonance Raman spectra of 1b-9b are all characteristic of the diamagnetic bis(mu-oxo)dicopper(lll) core. The intense ligand-to-metal charge transfer absorption maxima of CD-based Os are red-shifted proportionally with increasing peripheral ligand bulk, an effect ascribed to a slight distortion of the [Cu(2)O(2)] rhomb. The well-ordered crystal structure of [(L(ME))(2)Cu(2)(mu-O)(2)](CF(3)SO(3))(2)(.)4CH(2)Cl(2) ([3b(.)4CH(2)Cl(2)]) features the most metrically compact [Cu(2)O(2)](2+) core among structurally characterized Os (av Cu-O 1.802(7) angstrom; Cu(...)Cu 2.744(l) angstrom) and exemplifies the minimal square-planar ligation environment necessary for stabilization of Cu(lll). The reported Os are mild oxidants with moderate reactivity toward coordinating substrates, readily oxidizing thiols, certain activated alkoxides, and electron-rich phenols in a net 2e(-), 2H(+) process. In the absence of substrates, 1b-9b undergo thermally induced autolysis with concomitant degradation of the polyamine ligands. Ligand product distribution and primary kinetic isotope effects (k(osb)(H)/k(obs)(D) approximate to 8, (.)1b/d(24)-1b, 293 K) support a unimolecular mechanism involving rate-determining C-H bond cleavage at accessible ligand N-alkyl substituents. Decomposition half-lives span almost 3 orders of magnitude at 293 K, ranging from similar to 2 s for 4b to almost 30 min for d(24)-1b, the most thermally robust clicationic O yet reported. Dealkylation is highly selective where ligand rigidity constrains accessibility; in 3b, the ethyl groups are attacked preferentially. The observed relative thermal stabilities and dealkylation selectivities of 1b-9b are correlated with NC(alpha)-H bond dissociation energies, statistical factors, ligand backbone rigidity, and ligand denticity/axial donor strength. Among the peralkylated amines surveyed, bidentate ligands with oxidatively robust NC(alpha)-H bonds provide optimal stabilization for Os. Fortuitously, the least sterically demanding N-alkyl substituent methyl) gives rise to the most thermally stable and most physically accessible O core, retaining the potential for exogenous substrate reactivity.
