Oxidative Cyclization of a Phenolic Schiff Base and Synthesis of a Cyclometalated Ruthenium Nitrosyl Complex: Photoinduced NO Release by Visible Light
Oxidative Cyclization of a Phenolic Schiff Base and Synthesis of a Cyclometalated Ruthenium Nitrosyl Complex: Photoinduced NO Release by Visible Light
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DOI：
10.1021/ic1009847
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发表时间：
2010-08-16
影响因子：
4.6
通讯作者：
Goel, Nidhi
中科院分区：
文献类型：
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作者：
Ghosh, Kaushik;Kumar, Sushil;Goel, Nidhi
σ-芳基钌环金属盐 [Ru(L(SB1))(PPh(3))(2)Cl] 的反应活性 [1; L(SB1)H(2) = 4-甲基-2-(4-硝基亚苄基氨基)苯酚]与一氧化氮(NO)发生金属中心亚硝基化、环硝化和氧化环化，形成苯并恶唑衍生物。所得亚硝酰络合物的分子结构[Ru(L(PB1))(PPh(3))(2)(NO)Cl(ClO(4)) [2;测定了L(PB1)H = 5-甲基-7-硝基-2-(4-硝基苯基)苯并恶唑]，并对不同的σ-芳基钌环金属酸盐进行了表征，其中发现苯并恶唑衍生物与金属中心配位。晶体结构以及红外和核磁共振光谱数据证实了具有 S = 0 基态的抗磁性 {RuNO}(6) 物质的形成以及 {RuNO}(6) 部分的 {Ru(II)NO(+)}(6) 描述。所得复合物 2 中的配位 NO 在可见光下对光不稳定，并被转移为还原肌红蛋白。
The reactivity of sigma-arylruthenium cyclometallate [Ru(L(SB1))(PPh(3))(2)Cl] [1; L(SB1)H(2) = 4-methyl-2-(4-nitrobenzylideneamino)phenol] with nitric oxide (NO) gave rise to nitrosylation at the metal center, ring nitration, and oxidative cyclization, affording benzoxazole derivative formation. The molecular structure of the resultant nitrosyl complex,[Ru(L(PB1))(PPh(3))(2)(NO)Cl(ClO(4)) [2; L(PB1)H = 5-methyl-7-nitro-2-(4-nitrophenyl)benzoxazole]was determined, and a different sigma-arylruthenium cyclometallate was characterized in which the benzoxazole derivative was found to be coordinated to the metal center. The crystal structure and IR and NMR spectral data confirmed the formation of a diamagnetic {RuNO}(6) species with a S = 0 ground state and a {Ru(II)NO(+)}(6) description of the {RuNO}(6) moiety. Coordinated NO in the resultant complex 2 was photolabile under visible light and was transferred to reduced myoglobin.