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Photochemical activation of ruthenium(II)-pyridylamine complexes having a pyridine- N -oxide pendant toward oxygenation of organic substrates
- Photochemical activation of ruthenium(II)-pyridylamine complexes having a pyridine- N -oxide pendant toward oxygenation of organic substrates
- Kojima T.; Nakayama K.; Sakaguchi M.; Ogura T.; Ohkubo K.; Fukuzumi S.
- Ewha Authors
- Shunichi Fukuzumi
- SCOPUS Author ID
- Shunichi Fukuzumi
- Issue Date
- Journal Title
- Journal of the American Chemical Society
- vol. 133, no. 44, pp. 17901 - 17911
- SCI; SCIE; SCOPUS
- Ruthenium(II)-acetonitrile complexes having η 3-tris(2- pyridylmethyl)amine (TPA) with an uncoordinated pyridine ring and diimine such as 2,2′-bipyridine (bpy) and 2,2′-bipyrimidine (bpm), [Ru II(η 3-TPA)(diimine)(CH 3CN)] 2+, reacted with m-chloroperbenzoic acid to afford corresponding Ru(II)-acetonitrile complexes having an uncoordinated pyridine-N-oxide arm, [Ru II(η 3-TPA-O)(diimine)(CH 3CN)] 2+, with retention of the coordination environment. Photoirradiation of the acetonitrile complexes having diimine and the η 3-TPA with the uncoordinated pyridine-N-oxide arm afforded a mixture of [Ru II(TPA)(diimine)] 2+, intermediate-spin (S = 1) Ru(IV)-oxo complex with uncoordinated pyridine arm, and intermediate-spin Ru(IV)-oxo complex with uncoordinated pyridine-N-oxide arm. A Ru(II) complex bearing an oxygen-bound pyridine-N-oxide as a ligand and bpm as a diimine ligand was also obtained, and its crystal structure was determined by X-ray crystallography. Femtosecond laser flash photolysis of the isolated O-coordinated Ru(II)-pyridine-N-oxide complex has been investigated to reveal the photodynamics. The Ru(IV)-oxo complex with an uncoordinated pyridine moiety was alternatively prepared by reaction of the corresponding acetonitrile complex with 2,6-dichloropyridine-N-oxide (Cl 2py-O) to identify the Ru(IV)-oxo species. The formation of Ru(IV)-oxo complexes was concluded to proceed via intermolecular oxygen atom transfer from the uncoordinated pyridine-N-oxide to a Ru(II) center on the basis of the results of the reaction with Cl 2py-O and the concentration dependence of the consumption of the starting Ru(II) complexes having the uncoordinated pyridine-N-oxide moiety. Oxygenation reactions of organic substrates by [Ru II(η 3-TPA-O)(diimine)(CH 3CN)] 2+ were examined under irradiation (at 420 ± 5 nm) and showed selective allylic oxygenation of cyclohexene to give cyclohexen-1-ol and cyclohexen-1-one and cumene oxygenation to afford cumyl alcohol and acetophenone. © 2011 American Chemical Society.
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