Structural Characterization and Intramolecular Aliphatic C−H Oxidation Ability of MIII(μ-O)2MIII Complexes of Ni and Co with the Hydrotris(3,5-dialkyl-4-X-pyrazolyl)borate Ligands Tpmath image (X=Me, H, Br) and Tpmath image



Reaction of the dinuclear MII–bis(μ-hydroxo) complexes of nickel and cobalt, [{MII(TpR)}2(μ-OH)2] (M=Ni; 3Ni, M=Co: 3Co), with one equivalent of H2O2 yields the corresponding MIII–bis(μ-oxo) complexes, [{MIII(TpR)}2(μ-O)2] (M=Ni; 2Ni, M=Co: 2Co). The employment of a series of Tpmath image (Tpmath image=hydrotris(3,5-dimethyl-4-X-1-pyrazolyl)borate; X=Me, H, Br) as a metal supporting ligand makes it possible to isolate and structurally characterize the thermally unstable MIII–bis(μ-oxo) complexes 2Ni and 2Co. Both the starting (3Ni and 3Co) and resulting complexes (2Ni and 2Co) contain five-coordinate metal centers with a slightly distorted square-pyramidal geometry. Characteristic features of the nickel complexes 2Ni, such as the two intense absorptions around 400 and 300 nm in the UV-visible spectra and the apparent diamagnetism, are very similar to those of the previously reported bis(μ-oxo) species of CuIII and NiIII with ligands other than TpR, whereas the spectroscopic properties of the cobalt complexes 2Co (i.e., paramagnetically shifted NMR signals and a single intense absorption appearing at 350 nm) are clearly distinct from those of the isostructural nickel compounds 2Ni. Thermal decomposition of 2Ni and 2Co results in oxidation of the inner saturated hydrocarbyl substituents of the TpR ligand. Large kH/kD values obtained from the first-order decomposition rates of the Tpmath image and Tpmath image derivatives of 2 evidently indicate that the rate-determining step is an hydrogen abstraction from the primary C−H bond of the methyl substituents, mediated by the MIII2–(μ-O)2 species. The nickel complex 2Ni shows reactivity about 103 times greater than that of the cobalt analogue 2Co. The oxidation ability of the MIII(μ-O)2MIII core should be affected by the hindered TpR ligand system, which can stabilize the +2 oxidation state of the metal centers.