Schoumacker Sébastien, Hamelin Olivier, 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 Dec 1;42(24):8110-6. doi: 10.1021/ic0346533.
Three manganese(II) complexes, namely [Mn(1)(ClO(4))(2)] (3), [Mn(1)(acac)(2)] (4), and [Mn(2)(1)(acac)(4)] (5), were isolated from solutions of Mn(ClO(4))(2) or Mn(acac)(2), and an easily accessible diimine ligand (1S,2S)-N,N'-bis-pyridin-2-ylmethylene-cyclohexane-1,2-diamine (1). Their structure was determined by X-ray crystallography, and these complexes proved to be catalysts for asymmetric sulfide oxidation by H(2)O(2). Enantiomeric excesses ranging from 5% to 62% were obtained with a variety of aryl alkyl sulfides. We also observed an interesting "chirality switch" effect by the achiral acac anion reversing the enantioselectivity of the complex [Mn(1)(ClO(4))(2)] from the S to the R sulfoxide enantiomer.
从高氯酸锰（II）或乙酰丙酮锰（II）的溶液中分离出了三种锰（II）配合物，即[Mn(1)(ClO(4))(2)]（3）、[Mn(1)(acac)(2)]（4）和[Mn(2)(1)(acac)(4)]（5），以及一种易于获得的二亚胺配体（1S，2S）-N，N'-双吡啶-2-基亚甲基-环己烷-1，2-二胺（1）。通过X射线晶体学确定了它们的结构，并且这些配合物被证明是过氧化氢不对称硫化物氧化反应的催化剂。使用多种芳基烷基硫化物时，对映体过量率在5%至62%之间。我们还观察到了一种有趣的“手性开关”效应，即非手性的乙酰丙酮阴离子将配合物[Mn(1)(ClO(4))(2)]的对映选择性从S-亚砜对映体反转到R-亚砜对映体。
