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Syntheses, Characterization, and Catalytic Ability in Alkane Oxygenation of Chloro(dimethyl sulfoxide)ruthenium(II) Complexes with Tris(2-pyridylmethyl)amine and Its Derivatives1,2

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journal contribution
posted on 2006-10-02, 00:00 authored by Motowo Yamaguchi, Hiroyuki Kousaka, Shinichi Izawa, Yoshiki Ichii, Takashi Kumano, Dai Masui, Takamichi Yamagishi
New ruthenium(II) complexes having a tetradentate ligand such as tris(2-pyridylmethyl)amine (TPA), tris[2-(5-methoxycarbonyl)pyridylmethyl]amine [5-(MeOCO)3-TPA], tris(2-quinolylmethyl)amine (TQA), or bis(2-pyridylmethyl)glycinate (BPG) have been prepared. The reaction of the ligand with [RuCl2(Me2SO)4] resulted in a mixture of trans and cis isomers of the chloro(dimethyl sulfoxide-κS)ruthenium(II) complexes containing a TPA or a BPG, whereas a trans(Cl,Namino) isomer was selectively obtained for 5-(MeOCO)3-TPA and TQA. The trans and cis isomers of the [RuCl(TPA)(Me2SO)]+ complex were easily separated by fractional recrystallization. The molecular structures of trans- and cis(Cl,Namino)-[RuCl(TPA)(Me2SO)]+ complexes and the trans(Cl,Namino)-[RuCl{5-(MeOCO)3-TPA}(Me2SO)]+ complex have been determined by X-ray structural analyses. The reaction of TPA with [RuCl2(PhCN)4] gave a single isomer of the chloro(benzonitrile)ruthenium(II) complex, whereas the bis(benzonitrile)ruthenium(II) complex was obtained with BPG. The cis(Cl,Namino)-[RuCl(TPA)(Me2SO)]+ complex is thermodynamically much less stable than the trans isomer and isomerizes in dimethyl sulfoxide at 65−100 °C. Oxygenation of alkanes catalyzed by these ruthenium(II) complexes has been examined. The chloro(dimethyl sulfoxide-κS)ruthenium(II) complexes with TPA and its derivatives using m-chloroperbenzoic acid as a cooxidant showed high catalytic ability. Adamantane was efficiently and selectively oxidized to give 1-adamantanol up to 88%. The chloro(dimethyl sulfoxide-κS)ruthenium(II) complex with 5-(MeOCO)3-TPA was found to be the most active catalyst among the complexes examined.


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