Characterization of the Initial Intermediate Formed during Photoinduced Oxygenation of the Ruthenium(II) Bis(bipyridyl)flavonolate Complex
Characterization of the Initial Intermediate Formed during Photoinduced Oxygenation of the Ruthenium(II) Bis(bipyridyl)flavonolate Complex
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DOI：
10.1021/acs.inorgchem.6b00852
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发表时间：
2016-08-01
影响因子：
4.6
通讯作者：
Farmer, Patrick J.
中科院分区：
文献类型：
--
作者：
Han, Xiaozhen;Klausmeyer, Kevin K.;Farmer, Patrick J.
合成了一种黄酮醇钌配合物[Ru-II（bpy）（2）弗拉][BF 4]，用于模拟黄酮醇双加氧酶的反应性。在光下用分子氧处理[Ru-II（bpy）（2）弗拉] [BF 4]的干燥CH 3 CN溶液导致配位底物黄酮醇盐的氧化O-杂环开环，导致形成[Ru-II（bpy）（2）（carboxylate）][BF 4]（carboxylate = O-苯甲酰水杨酸盐或苯甲酸盐）物种，如通过电喷雾电离质谱测定的。适度的激发和温度允许分离和表征的中间体，[Ru-II（bpy）（2），bpg][BF 4]（bpg = 2-苯甲酰氧基苯乙醛酸），产生的1，2-加成的双氧的中心黄酮环。
A ruthenium(II) flavonolate complex, [Ru-II(bpy)(2)fla][BF4], was synthesized to model the reactivity of the flavonol dioxygenases. The treatment of dry CH3CN solutions of [Ru-II(bpy)(2)fla] [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)(2),bpg][BF4] (bpg = 2-benzoyloxyphenylglyoxylate), generated by the 1,2-addition of dioxygen to the central flavonolate ring.