title: Facile metalation of silicon and germanium analogues of thiocarboxylic acids with a manganese(II) hydride precursor.
abstract: Synthesis and characterization of the first manganese(II)-containing heavier thiocarboxylate analogues, [L(Dip)Si(=S)OMnL(Dep)] (4; L(Dip)=CH[C(Me)N(2,6-iPr(2)C(6)H(3))](2), L(Dep)=CH[C(Me)N(2,6-Et(2)C(6)H(3))](2)) and [L(Dip)Ge(=S)OMnL(Dep)] (5) are described. They are accessible through reaction of the silicon and germanium analogues of the respective thiocarboxylic acids [L(Dip)E(=S)OH] (E=Si, Ge) with the β-diketiminato (nacnac) manganese(II) hydride precursor [(L(Dep)Mn)(2)(μ-H)(2)] (3) in high yield. The first Mn nacnac hydride 3 has been prepared by the reaction of manganese bromide [(L(Dep)Mn)(2)(μ-Br)(2)] (2) with KBEt(3)H. Compounds 4 and 5 represent the first transition-metal heavier thiocarboxylates with the Si=S and Ge=S functionalities. All new compounds are paramagnetic and were characterized by elemental analysis, IR spectroscopy, MS (EI), and single-crystal X-ray diffraction analyses. Due to the N→E (E=Si, Ge) and E=S→Mn donor-acceptor interaction as well as the carboxylate-like π-electron delocalization within the E(S)O moieties, the E=S double bonds in these compounds are resonance stabilized.
authors: Institute of Chemistry, Metalorganics and Inorganic Materials, Sekr. C2, Technische Universität Berlin, Strasse des 17. Juni 135, 10623 Berlin, Germany.
authors: Shenglai
authors: S
authors: Yao
authors: Yun
authors: Y
authors: Xiong
authors: Matthias
authors: M
authors: Driess
mesh_terms: D002264:Carboxylic Acids / Q000737:chemistry*; D018360:Crystallography, X-Ray; D005857:Germanium / Q000737:chemistry*; D008345:Manganese / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D012825:Silicon / Q000737:chemistry*; D013438:Sulfhydryl Compounds / Q000737:chemistry*
chemical_list: D002264:Carboxylic Acids; D009942:Organometallic Compounds; D013438:Sulfhydryl Compounds; D005857:Germanium; D008345:Manganese; D012825:Silicon