Tris[(4-methylphenyl)sulfanyl]silane | 129943-29-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: Tris[(4-methylphenyl)sulfanyl]silane
• 英文别名: tris[(4-methylphenyl)sulfanyl]silane
• CAS: 129943-29-9
• 化学式: C₂₁H₂₂S₃Si
• 分子量: 398.689
• InChiKey: VBUIGZKHQVWGDJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.01
• 重原子数：
  25
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  75.9
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  Tris[(4-methylphenyl)sulfanyl]silane 、 (η5-C5Me5)(PMe3)2Ru(CH2SiMe3) 以 甲苯 为溶剂， 以85%的产率得到{(η5-C5Me5)(PMe3)2RuSi(S-p-C6H4CH3)3}
  参考文献：
  名称：

  碱稳定的亚甲硅烷基配合物的合成，结构和动力学研究

  摘要：

  The silyl complexes Cp*(PMe(3))(2)RuSiX(2)Z (Cp* = eta(5)-C(5)Me(5); 1, SiX(2)Z = Si[S(Tol-p)](3); 2, SIX(2)Z = Si[O(Tol-p)](3); 3, SiX(2)Z = SiMe(2)[S(Tol-p)]), prepared by reaction of the appropriate hydrosilane with Cp* (PMe(3))(2)RuCH(2)SiMe(3), react with Me(3)SiOTf (OTf = OSO2CF3) to afford the triflato(silyl) complexes Cp*(PMe(3))(2)RuSiX(2)OTf (4, X = S(Tol-p); 5, X = O(Tol-p); 6, X = Me) or Cp*(PMe(3))(2)Rusi[S(Tol-p)](OTf)(2) (7). The X-ray crystal structures of the compounds 1, 4, and 7 are described and discussed. Compound 4 reacts with LiBEt(3)H to produce Cp*(PMe(3))(2)RuSiH[S(Tol-p)](2) (8), with water to give Cp*(PMe(3))(2)RuSi[S(Tol-p)](OTf)(OH) (10), and with HCl to afford Cp*(PMe(3))(2) RuSiCl2(OTf) (11). The triflate Cp*(PMe(3))(2)RuSiH[S(Tol-p)](OTf) (9) results from reaction of 8 with Me(3)SiOTf. The base-stabilized silylene complexes [Cp*(PMe(3))2Ru SiX(2)(NCMe)]BPh(4) (13, X = S(Tol-p); 14, X = O(Tol-p); 15, X = Me) are prepared by displacement of triflate from 4-6. The X-ray structures of 13 and 15 are described and compared to the previously reported structure of [Cp*(PMe(3))(2)RuSiPh(2)(NCMe)]BPh(4) (12). The structures are discussed in terms of the amount of incipient silylene character possessed by each. For 12-15, bound acetonitrile exchanges with free acetonitrile in dichloromethane solution via a dissociative mechanism. The rates and activation parameters for these exchange reactions allow an ordering of stabilities for the corresponding base-free silylene complexes, since the reactions involve rate-limiting loss of acetonitrile from the complex. The kinetic data indicate that the stabilizing influences for silylene substituents in this system are ordered according to : S(Tol-p) > O(Tol-p) > Me > Ph. A different ordering is suggested by the X-ray structural data. Apparently conflicting information from the structural and dynamic studies are discussed and rationalized, and it is concluded that the ordering suggested by the kinetic data is more useful.

  DOI：

  10.1016/0277-5387(94)00367-n

文献信息

• Osmium Alkyl and Silyl Derivatives with Cyclopentadienyl(phosphine) and Pentamethylcyclopentadienyl(phosphine) Ligand Sets
  作者：Paulus W. Wanandi、T. Don Tilley

  DOI：10.1021/om9704197

  日期：1997.9.1

  triflate complex Cp(PPh3)2OsOTf (2), which possesses a labile triflate group. The structure of complex 2 was determined by X-ray crystallography. Similar to their ruthenium analogs, the osmium(II) alkyl complexes 4, 5, and 7 thermally activate arene C−H bonds. Reaction of 7 with HSiR2[S(p-Tol)] (R = S(p-Tol), Me) provides metallacycle complexes of the = S(p-Tol) (11), Me (13)) via activation of both

  描述了含有环戊二烯基（膦）和五甲基环戊二烯基（膦）配体对的新型（Ⅱ）和（Ⅳ）甲硅烷基衍生物的制备和表征。hydro硅烷基络合物是通过氢化硅烷与Cp'（PR 3）2 OsCH 2 SiMe 3（Cp'= Cp，R = Ph（4），Me（5）; CP” =η 5 -C 5我5，R =我（7）），而这又是通过相应的溴配合物烷基化可用。Cp（PR 3）2的烷基衍生物的合成Os（R = Ph，Me）需要使用二烷基镁试剂，而更富电子的Cp *（PMe 3）2 Os系统的烷基化可以使用格氏试剂来实现。另外，Cp（PPh 3）2 OsBr与AgOTf（Tf = SO 2 CF 3）的反应产生了三氟甲磺酸）（II）复合物Cp（PPh 3）2 OsOTf（2），它具有不稳定的三氟甲磺酸酯基。配合物2的结构通过X射线晶体学确定。类似于它们钌类似物，锇（II）配合物的烷基4，5，和7热活化芳烃CH键。的反应7与HSIR
• Synthesis, structure and dynamic studies on base-stabilized silylene complexes
  作者：Steven K. Grumbine、Daniel A. Straus、T. Don Tilley、Arnold L. Rheingold

  DOI：10.1016/0277-5387(94)00367-n

  日期：1995.1

  The silyl complexes Cp*(PMe(3))(2)RuSiX(2)Z (Cp* = eta(5)-C(5)Me(5); 1, SiX(2)Z = Si[S(Tol-p)](3); 2, SIX(2)Z = Si[O(Tol-p)](3); 3, SiX(2)Z = SiMe(2)[S(Tol-p)]), prepared by reaction of the appropriate hydrosilane with Cp* (PMe(3))(2)RuCH(2)SiMe(3), react with Me(3)SiOTf (OTf = OSO2CF3) to afford the triflato(silyl) complexes Cp*(PMe(3))(2)RuSiX(2)OTf (4, X = S(Tol-p); 5, X = O(Tol-p); 6, X = Me) or Cp*(PMe(3))(2)Rusi[S(Tol-p)](OTf)(2) (7). The X-ray crystal structures of the compounds 1, 4, and 7 are described and discussed. Compound 4 reacts with LiBEt(3)H to produce Cp*(PMe(3))(2)RuSiH[S(Tol-p)](2) (8), with water to give Cp*(PMe(3))(2)RuSi[S(Tol-p)](OTf)(OH) (10), and with HCl to afford Cp*(PMe(3))(2) RuSiCl2(OTf) (11). The triflate Cp*(PMe(3))(2)RuSiH[S(Tol-p)](OTf) (9) results from reaction of 8 with Me(3)SiOTf. The base-stabilized silylene complexes [Cp*(PMe(3))2Ru SiX(2)(NCMe)]BPh(4) (13, X = S(Tol-p); 14, X = O(Tol-p); 15, X = Me) are prepared by displacement of triflate from 4-6. The X-ray structures of 13 and 15 are described and compared to the previously reported structure of [Cp*(PMe(3))(2)RuSiPh(2)(NCMe)]BPh(4) (12). The structures are discussed in terms of the amount of incipient silylene character possessed by each. For 12-15, bound acetonitrile exchanges with free acetonitrile in dichloromethane solution via a dissociative mechanism. The rates and activation parameters for these exchange reactions allow an ordering of stabilities for the corresponding base-free silylene complexes, since the reactions involve rate-limiting loss of acetonitrile from the complex. The kinetic data indicate that the stabilizing influences for silylene substituents in this system are ordered according to : S(Tol-p) > O(Tol-p) > Me > Ph. A different ordering is suggested by the X-ray structural data. Apparently conflicting information from the structural and dynamic studies are discussed and rationalized, and it is concluded that the ordering suggested by the kinetic data is more useful.