title: Structural characterization and intramolecular aliphatic C-H oxidation ability of M(III)(mu-O)2M(III) complexes of Ni and Co with the hydrotris-(3,5-dialkyl-4-X-pyrazolyl)borate ligands TpMe2,X (X = Me, H, Br) and TpiPr2.
abstract: Reaction of the dinuclear M(II)-bis(mu-hydroxo) complexes of nickel and cobalt, [(M(II)(TpR)]2(mu-OH)2] (M = Ni; 3Ni M = Co: 3Co), with one equivalent of H2O2 yields the corresponding M(III)-bis(mu-oxo) complexes, [[M(III)(TpR)]2-(mu-O)2] (M=Ni; 2Ni, M=Co: 2Co). The employment of a series of TpMe2,X (TpMe2,X = 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 M(III)-bis-(mu-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(mu-oxo) species of Cu(III) and Ni(III) 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 TpMe3 and Tp(CD3)2,Me 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 M(III)2-(mu-O)2 species. The nickel complex 2Ni shows reactivity about 10(3) times greater than that of the cobalt analogue 2Co. The oxidation ability of the M(III)(mu-O)2M(III) core should be affected by the hindered TpR ligand system, which can stabilize the +2 oxidation state of the metal centers.
authors.affiliation: Chemical Resources Laboratory, Tokyo Institute of Technology, Yokohama, Japan. shikichi@res.titech.ac.jp
authors.forename: S
authors.initials: S
authors.lastname: Hikichi
authors.forename: M
authors.initials: M
authors.lastname: Yoshizawa
authors.forename: Y
authors.initials: Y
authors.lastname: Sasakura
authors.forename: H
authors.initials: H
authors.lastname: Komatsuzaki
authors.forename: Y
authors.initials: Y
authors.lastname: Moro-oka
authors.forename: M
authors.initials: M
authors.lastname: Akita
mesh_terms: D003035:Cobalt / Q000737:chemistry*; D018360:Crystallography, X-Ray; D008024:Ligands; D008667:Metalloproteins / Q000737:chemistry; D015394:Molecular Structure; D009532:Nickel / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D010100:Oxygen / Q000378:metabolism*; D013057:Spectrum Analysis
chemical_list: D008024:Ligands; D008667:Metalloproteins; D009942:Organometallic Compounds; D003035:Cobalt; D009532:Nickel; D010100:Oxygen