title: Synthesis and characterization of mononuclear ruthenium(III) pyridylamine complexes and mechanistic insights into their catalytic alkane functionalization with m-chloroperbenzoic acid.
abstract: A series of mononuclear RuIII complexes [RuCl2(L)]+, where L is tris(2-pyridylmethyl)amine (TPA) or one of four TPA derivatives as tetradentate ligand, were prepared and characterized by spectroscopic methods, X-ray crystallography, and electrochemical measurements. The geometry of a RuIII complex having a non-threefold-symmetric TPA ligand bearing one dimethylnicotinamide moiety was determined to show that the nicotine moiety resides trans to a pyridine group, but not to the chlorido ligand. The substituents of the TPA ligands were shown to regulate the redox potential of the ruthenium center, as indicated by a linear Hammett plot in the range of 200 mV for RuIII/RuIV couples with a relatively large rho value (+0.150). These complexes act as effective catalysts for alkane functionalization in acetonitrile with m-chloroperbenzoic acid (mCPBA) as terminal oxidant at room temperature. They exhibited fairly good reactivity for oxidation of cyclohexane (C--H bond energy 94 kcal mol(-1)), and the reactivity can be altered significantly by the electronic effects of substituents on TPA ligands in terms of initial rates and turnover numbers. Catalytic oxygenation of cyclohexane by a RuIII complex with 16O-mCPBA in the presence of H2 18O gave 18O-labeled cyclohexanol with 100% inclusion of the 18O atom from the water molecule. Resonance Raman spectra under catalytic conditions without the substrate indicate formation of a RuIV==O intermediate with lower bonding energy. Kinetic isotope effects (KIEs) in the oxidation of cyclohexane suggest that hydrogen abstraction is the rate-determining step and the KIE values depend on the substituents of the TPA ligands. Thus, the reaction mechanism of catalytic cyclohexane oxygenation depends on the electronic effects of the ligands.
authors.affiliation: Department of Chemistry, Faculty of Sciences, Kyushu University, Hakozaki, Higashi-Ku, Fukuoka 812-8581, Japan. kojima@chem.eng.osaka-u.ac.jp
authors.forename: Takahiko
authors.initials: T
authors.lastname: Kojima
authors.forename: Ken-ichi
authors.initials: K
authors.lastname: Hayashi
authors.forename: Shin-ya
authors.initials: SY
authors.lastname: Iizuka
authors.forename: Fumito
authors.initials: F
authors.lastname: Tani
authors.forename: Yoshinori
authors.initials: Y
authors.lastname: Naruta
authors.forename: Masaki
authors.initials: M
authors.lastname: Kawano
authors.forename: Yuji
authors.initials: Y
authors.lastname: Ohashi
authors.forename: Yuichirou
authors.initials: Y
authors.lastname: Hirai
authors.forename: Kei
authors.initials: K
authors.lastname: Ohkubo
authors.forename: Yoshihisa
authors.initials: Y
authors.lastname: Matsuda
authors.forename: Shunichi
authors.initials: S
authors.lastname: Fukuzumi