title: Characterization of the Initial Intermediate Formed during Photoinduced Oxygenation of the Ruthenium(II) Bis(bipyridyl)flavonolate Complex.
abstract: A ruthenium(II) flavonolate complex, [Ru(II)(bpy)2fla][BF4], was synthesized to model the reactivity of the flavonol dioxygenases. The treatment of dry CH3CN solutions of [Ru(II)(bpy)2fla][BF4] with dioxygen under light leads to the oxidative O-heterocyclic ring opening of the coordinated substrate flavonolate, resulting in the formation of [Ru(II)(bpy)2(carboxylate)][BF4] (carboxylate = O-benzoylsalicylate or benzoate) species, as determined by electrospray ionization mass spectrometry. Moderation of the excitation and temperature allowed isolation and characterization of an intermediate, [Ru(II)(bpy)2bpg][BF4] (bpg = 2-benzoyloxyphenylglyoxylate), generated by the 1,2-addition of dioxygen to the central flavonolate ring.
authors.affiliation: Department of Chemistry and Biochemistry, Baylor University , Waco, Texas 76798, United States.
authors.forename: Xiaozhen
authors.initials: X
authors.lastname: Han
authors.affiliation: Department of Chemistry and Biochemistry, Baylor University , Waco, Texas 76798, United States.
authors.forename: Kevin K
authors.initials: KK
authors.lastname: Klausmeyer
authors.affiliation: Department of Chemistry and Biochemistry, Baylor University , Waco, Texas 76798, United States.
authors.forename: Patrick J
authors.initials: PJ
authors.lastname: Farmer
mesh_terms: D018360:Crystallography, X-Ray; D049308:Dioxygenases / Q000737:chemistry* / Q000378:metabolism; D008024:Ligands; D008027:Light; D009682:Magnetic Resonance Spectroscopy; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry; D012428:Ruthenium / Q000737:chemistry*; D021241:Spectrometry, Mass, Electrospray Ionization; D013055:Spectrophotometry, Infrared
chemical_list: D008024:Ligands; D009942:Organometallic Compounds; D012428:Ruthenium; D049308:Dioxygenases; D010100:Oxygen