(PhSCH₂SiMe₂)₂O | 2096-56-2

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: (PhSCH₂SiMe₂)₂O
• 英文别名: 1,3-Bis-phenylthiomethyl-1,1,3,3-tetramethyl-disiloxan；[Dimethyl(phenylsulfanylmethyl)silyl]oxy-dimethyl-(phenylsulfanylmethyl)silane
• CAS: 2096-56-2
• 化学式: C₁₈H₂₆OS₂Si₂
• 分子量: 378.707
• InChiKey: KBSNFJRDWCQSQR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.08
• 重原子数：
  23
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  59.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  茴香硫醚 、 二氯二甲基硅烷 在 正丁基锂 作用下， 以 乙醚 、 环己烷 为溶剂， 以85%的产率得到(PhSCH₂SiMe₂)₂O
  参考文献：
  名称：

  Reinvestigation of the Pd-catalyzed bis(silylation) of alkynes with 1,1,2,2-tetramethyl-1,2-bis(phenylthiomethyl)disilane: Unexpected formation of the eight-membered siloxane–chelate complex cis-[PdCl2{(PhSCH2SiMe2)2O}]

  摘要：

  The bis(silylated) alkenes Z-(PhSCH2)Me2SiC(H)= C(Fc)SiMe2(CH2SPh) (2) and Z-(PhSCH2)Me2SiC(H)= C(bipheny)SiMe2(CH2SPh) (3) have been prepared by Pd-catalyzed double silylation of ethynylferrocene and 4-ethynyl-1,1'-biphenyl in the presence of 1,1,2,2-tetramethyl-1,2-bis(phenylthiomethyl)disilane (1). A reinvestigation on the interaction of 1 with [PdCl2(PhCN)(2)] in technical-grade CH2Cl2 as solvent revealed competition between reduction to elemental palladium (due to oxidative addition of the Si-Si bond across Pd(II) and subsequent reductive elimination) and formation of an unusual eight-membered chelate complex cis-[PdCl2{(PhSCH2SiMe2)(2)O}] (4), which is fluxional in solution. Based on GC-MS analyses revealing both formation of chlorosilane ClSiMe2CH2SPh and the disiloxane (PhSCH2SiMe2)(2)O, residual water contained in CH2Cl2 is supposed to be the source for the oxygen atom of the siloxane function. The mechanism of the formation of 4 is discussed. The molecular structures of 1 and 4 were determined by single-crystal X-ray diffraction analyses. The energies of several conformational isomers of 4 were computed by means of DFT calculations, the coexistence of a species featuring a weak dative Pd-O interaction due to a hemi-labile coordination of ligand 1 was evidenced. (C) 2012 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2012.11.022