title: Four-electron oxidative dehydrogenation induced by proton-coupled electron transfer in ruthenium(III) complex with 2-(1,4,5,6-tetrahydropyrimidin-2-yl)phenolate.
abstract: New ruthenium(II or III) complexes with general formula [Ru(O-N)(bpy)2](n+) (O-N = unsymmetrical bidentate phenolate ligand; bpy = 2,2'-bipyridine) were synthesized, and their crystal structures and electrochemical properties were characterized. Ru(II) complexes with 2-(2-imidazolinyl)phenolate (Himn(-)) or 2-(1,4,5,6-tetrahydropyrimidin-2-yl)phenolate (Hthp(-)) could be deprotonated by addition of excess KO(t)Bu, although the deprotonated species were easily reprotonated by exposure to air. Unlike these Ru(II) complexes, their Ru(III) analogs showed interesting ligand oxidation reactions upon addition of bases. With [Ru(III)(Himn)(bpy)2](2+), two-electron oxidation of Himn(-) and reduction of the Ru(III) center resulted in conversion of the 2-imidazolinyl group to a 2-imidazolyl group. On the other hand, the corresponding Hthp(-) complex exhibited four-electron oxidation of the ligand to form 2-(2-pyrimidyl)phenolate (pym(-)). These aromatization reactions of imidazolinyl and 1,4,5,6-tetrahydropyrimidyl groups were also achieved by the electrochemically generated Ru(III) complexes.
authors: Department of Chemistry, Graduate School of Natural Science and Technology, Okayama University, 3-1-1 Tsushima-naka, Kita-ku, Okayama 700-8530, Japan. mitsuhashi@s.okayama-u.ac.jp
authors: Ryoji
authors: R
authors: Mitsuhashi
authors: Takayoshi
authors: T
authors: Suzuki
authors: Yukinari
authors: Y
authors: Sunatsuki