Association of Oxo-Molybdenum Dithiolene Complexes with a Multiamide Additive and Its Influence on the Ease of O-Atom Transfer.
Association of Oxo-Molybdenum Dithiolene Complexes with a Multiamide Additive and Its Influence on the Ease of O-Atom Transfer.
复制标题
氧代二硫醇钼配合物与多酰胺添加剂的缔合及其对氧原子转移容易程度的影响。
作者：
H. Oku;N. Ueyama;A. Nakamura
为了调节二硫烯二氧代钼（VI）络合物的反应性，研究了两个系统：（1）用二酰胺添加剂1,3-双（异丁酰氨基）苯（1）进行螯合物识别； (2) 具有四个酰胺取代基的二硫醇络合物，(n-Pr(4)N)(2)[Mo(IV)O{S(2)C(2)(CONH(2))(2)}(2)].0.5(i-PrOH).DMF (2) (S(2)C(2)(CONH(2))(2) = 1,2-二氨基甲酰亚乙基-1,2-二硫醇盐）。两种酰胺化合物，即添加剂 1 和络合物 2，均设计为与 (Mo(VI)O(2))(2+) 和 (Mo(IV)O)(2+) 络合物中的硫醇盐配体形成 NH.S 和/或 NH.O 氢键。滴定分析表明CH(2)Cl(2) 溶液中存在1:1 络合物。这种缔合导致钼络合物的溶解度和反应性发生变化。当添加剂与 (NEt(4))(2)[Mo(IV)O{S(2)C(2)(COOMe)(2)}(2)] (3) (S(2)C(2)(COOMe)(2) = 1,2-二(甲氧基羰基)亚乙基-1,2-二硫醇盐) 的 DMSO-d(6) 溶液混合时，Me(3)NO 的还原率增加了6. 还观察到化合物 2 的加速。看来 NH.S 氢键正在调节系统。
To regulate the reactivity of dithiolene dioxomolybdenum(VI) complexes, two systems were studied: (1) chelate recognition with a diamide additive, 1,3-bis(isobutyrylamino)benzene (1); (2) a dithiolene complex with four amide substituents, (n-Pr(4)N)(2)[Mo(IV)O{S(2)C(2)(CONH(2))(2)}(2)].0.5(i-PrOH).DMF (2) (S(2)C(2)(CONH(2))(2) = 1,2-dicarbamoylethylene-1,2-dithiolate). Both amide compounds, the additive 1 and the complex 2, were designed to form NH.S and/or NH.O hydrogen bonding with thiolate ligands in (Mo(VI)O(2))(2+) and (Mo(IV)O)(2+) complexes. Titration analyses indicate the presence of a 1:1 complex in CH(2)Cl(2) solution. This association causes changes in solubility and reactivity of the molybdenum complexes. When the additive was mixed with a DMSO-d(6) solution of (NEt(4))(2)[Mo(IV)O{S(2)C(2)(COOMe)(2)}(2)] (3) (S(2)C(2)(COOMe)(2) = 1,2-di(methoxycarbonyl)ethylene-1,2-dithiolate), the rate of reduction of Me(3)NO was increased by a factor of 6. An acceleration was also observed for compound 2. It appeares that NH.S hydogen bonding is modulating the system.