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Chiral eta(6)-Arene/N-Tosylethylenediamine-Ruthenium(II) Complexes: Solution Behavior and Catalytic Activity for Asymmetric Hydrogenation
其他题名手性芳烃/N-苯磺酰基乙二胺钌(Ⅱ)配合物: 其溶液性质及不对称催化氢化研究
克里斯蒂安.山多夫; Bie FS(别福升); 松冈亚希; 山口芳树; Bo NK(博那珂); Li YH(李跃辉); Jia T(加藤); 范之内海; Di BY(堤邦彦); 武Ohkuma; 村田邦彦; 野依良治
2010
发表期刊Chem.-Asian J.
ISSN1861-4728
卷号5期号:4页码:806-816
摘要Aromatic ketones are enantioseletively hydrogenated in alcohols containing [RuX{(S,S)-Tsdpen)(eta(6)-p-cymene)] (Tsdpen=TsNCH(C6H5)CH-(C6H3)NH2; X = TfO, Cl) as precatalysts. The corresponding Ru hydride (X = H) acts as a reducing species. The solution structures and complete spectral assignment of these complexes have been determined using 2D NMR (H-1-H-1 DQF-COSY, H-1-C-13 HMQC, HSQC, and H-1-F-19 HOESY). Depending on the nature of the solvents and conditions, the precatalysts exist as a covalently bound complex, tight ion pair of [Ru+(Tsdpen)(cymene)] and X-, solvent-separated ion pair, or discrete free ions. Solvent effects on the NH2 chemical shifts of the Ru complexes and the hydrodynamic radius and volume of the Re and TfO- ions elucidate the process of precatalyst activation for hydrogenation. Most notably, the Ru triflate possessing a high ionizability, substantiated by cyclic voltammetry, exists in alcoholic solvents largely as a solvent-separated ion pair and/or free ions. Accordingly, its diffusion-derived data in CD3OD reflect the independent motion of [Ru+(Tsdpen)(cymene) and TfO-. In CDCl3, the complex largely retains the covalent structure showing similar diffusion data for the cation and anion. The Ru triflate and chloride show similar but distinct solution behavior in various solvents. Conductivity measurements and catalytic behavior demonstrate that both complexes ionize in CH3OH to generate a common [Ru+(Tsdpen)(cymene)] and X-, although the extent is significantly greater for X = TfO-. The activation of [RuX(Tsdpen)(cymene)] during catalytic hydrogenation in alcoholic solvent occurs by simple ionization to generate [Ru+(Tsdpen)(cymene)]. The catalytic activity is thus significantly influenced by the reaction conditions.
学科领域金属有机化学
部门归属名古屋大学; 中国科学院上海有机化学研究所; 上海大学; 名古屋市立大学; 关东化工有限责任公司; 北海道大学
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收录类别SCI
语种英语
WOS记录号WOS:000276641400013
引用统计
文献类型期刊论文
条目标识符http://ir.sioc.ac.cn/handle/331003/27797
专题上海有机化学研究所
通讯作者克里斯蒂安.山多夫; 野依良治
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克里斯蒂安.山多夫,Bie FS,松冈亚希,et al. Chiral eta(6)-Arene/N-Tosylethylenediamine-Ruthenium(II) Complexes: Solution Behavior and Catalytic Activity for Asymmetric Hydrogenation[J]. Chem.-Asian J.,2010,5(4):806-816.
APA 克里斯蒂安.山多夫.,别福升.,松冈亚希.,山口芳树.,博那珂.,...&野依良治.(2010).Chiral eta(6)-Arene/N-Tosylethylenediamine-Ruthenium(II) Complexes: Solution Behavior and Catalytic Activity for Asymmetric Hydrogenation.Chem.-Asian J.,5(4),806-816.
MLA 克里斯蒂安.山多夫,et al."Chiral eta(6)-Arene/N-Tosylethylenediamine-Ruthenium(II) Complexes: Solution Behavior and Catalytic Activity for Asymmetric Hydrogenation".Chem.-Asian J. 5.4(2010):806-816.
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