Chavarot Murielle, Ménage Stéphane, Hamelin Olivier, Charnay Florence, Pécaut Jacques, Fontecave Marc
Laboratoire de Chimie et Biochimie des Centres Rédox Biologiques, DRDC-CB, UMR 5047, Université Joseph Fourier/CEA/CNRS, CEA Grenoble, 17 avenue des martyrs, 38054 Grenoble Cedex, France.
Inorg Chem. 2003 Aug 11;42(16):4810-6. doi: 10.1021/ic0341338.
cis-[Ru(dmp)(2)(CH(3)CN)(2)]PF(6) (dmp = 2,9-dimethyl-1,10-phenanthroline), complex 1PF(6), exists in two enantiomeric forms, Delta and Lambda. During treatment with the chiral anion tris[tetrachlorobenzene-1,2-bis(olato)]phosphate(V), also named Trisphat, in dichloromethane it has been possible to selectively precipitate each enantiomer, associated with Trisphat in the form of the heterochiral pair. This enantiomerically pure compound has been characterized in solution by UV-visible, CD, ESI-MS, and NMR spectroscopy and by X-ray crystallography in the solid state. Trisphat was also used as an NMR chiral shift reagent to determine the enantiomeric excess of the complex preparations. The "chiral-at-metal" ruthenium complex has been evaluated as a catalyst for the oxidation of sulfides to sulfoxides by hydrogen peroxide. The reactions displayed a low but significant level of enantioselectivity (18% ee in the case of 4-bromophenyl methyl sulfide). Our results thus provide the first demonstration that the chiral information carried by a stereogenic metal center can be catalytically transferred to molecules during stereoselective oxidation.
顺式-[Ru(dmp)(2)(CH(3)CN)(2)]PF(6)（dmp = 2,9 - 二甲基 - 1,10 - 菲咯啉），即配合物1PF(6)，以两种对映体形式存在，Δ型和Λ型。在二氯甲烷中用手性阴离子三[四氯苯 - 1,2 - 双（醇盐）]磷酸酯（V）（也称为Trisphat）处理时，有可能选择性地沉淀出每种对映体，它们以异手性对的形式与Trisphat结合。这种对映体纯的化合物已通过紫外可见光谱、圆二色光谱、电喷雾电离质谱和核磁共振光谱在溶液中进行了表征，并通过X射线晶体学在固态下进行了表征。Trisphat还被用作核磁共振手性位移试剂来测定配合物制剂的对映体过量。“金属手性”钌配合物已被评估为用过氧化氢将硫化物氧化为亚砜的催化剂。这些反应表现出较低但显著的对映选择性水平（对于4 - 溴苯基甲基硫醚，对映体过量为18%）。因此，我们的结果首次证明了由手性金属中心携带的手性信息在立体选择性氧化过程中可以催化转移到分子上。
