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Facile Metalation of Silicon and Germanium Analogues of Thiocarboxylic Acids With a manganese(II) Hydride Precursor

Facile Metalation of Silicon and Germanium Analogues of Thiocarboxylic Acids With a manganese(II) Hydride Precursor

Shenglai Yao, Yun Xiong, Matthias Driess

Chemistry. 2012 Sep 3;18(36):11356-61.

PMID: 22829217

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.

Chemicals Related in the Paper:

Catalog Number	Product Name	Structure	CAS Number	Price
AP24415007	Germanium(II) bromide		24415-00-7	Price

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