%0 Generic %A Schoumacker, Sébastien %A Hamelin, Olivier %A Pécaut, Jacques %A Fontecave, Marc %D 2003 %T Catalytic Asymmetric Sulfoxidation by Chiral Manganese Complexes:  Acetylacetonate Anions as Chirality Switches %U https://acs.figshare.com/articles/dataset/Catalytic_Asymmetric_Sulfoxidation_by_Chiral_Manganese_Complexes_Acetylacetonate_Anions_as_Chirality_Switches/3358060 %R 10.1021/ic0346533.s003 %2 https://acs.figshare.com/ndownloader/files/5197366 %K Catalytic Asymmetric Sulfoxidation %K sulfide oxidation %K Chirality Switches %K achiral acac anion %K Mn 2 %K aryl alkyl sulfides %K Enantiomeric excesses %K H 2 O 2 %K R sulfoxide enantiomer %X Three manganese(II) complexes, namely [Mn(1)(ClO4)2] (3), [Mn(1)(acac)2] (4), and [Mn2(1)(acac)4] (5), were isolated from solutions of Mn(ClO4)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 H2O2. 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)(ClO4)2] from the S to the R sulfoxide enantiomer. %I ACS Publications