(phenylthio)tris(trimethyl-l5-phosphaneyl)rhodium | 148484-09-7

• 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: (phenylthio)tris(trimethyl-l5-phosphaneyl)rhodium
• CAS: 148484-09-7
• 化学式: C₁₅H₃₂P₃RhS
• 分子量: 440.312
• InChiKey: FEOQCMZDGXQMQL-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  6.31
• 重原子数：
  20.0
• 可旋转键数：
  5.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  (phenylthio)tris(trimethyl-l5-phosphaneyl)rhodium 以 甲苯 为溶剂， 以79%的产率得到trans,mer-RhH(SPh)2(PMe3)3
  参考文献：
  名称：

  Osakada, Kohtaro; Hataya, Kouji; Yamamoto, Takakazu, Inorganic Chemistry, 1993, vol. 32, # 11, p. 2360 - 2365

  摘要：

  DOI：
• 作为产物：
  描述：

  sodium thiophenolate 、 以 正己烷 为溶剂， 以22%的产率得到(phenylthio)tris(trimethyl-l5-phosphaneyl)rhodium
  参考文献：
  名称：

  Osakada, Kohtaro; Hataya, Kouji; Yamamoto, Takakazu, Inorganic Chemistry, 1993, vol. 32, # 11, p. 2360 - 2365

  摘要：

  DOI：

文献信息

• Unique intramolecular exchange between H of SiHPh2 and SAr in [RhH(SiHPh2)(SAr)(PMe3)3]
  作者：Kohtaro Osakada、Kouji Hataya、Takakazu Yamamoto

  DOI：10.1039/c39950002315

  日期：——

  mer-iRhH[SiHPh2(SAr)(PMe3)3], prepared from oxidative addition of H2SiPh2 to Rh(SAr)(PMe3)3, undergoes transfer of the thiolato ligand to the coordinated Si atom to give fac-[RhH2SiPh2(SAr)}(PMe3)3].

  由 H2SiPh2 与 Rh(SAr)(PMe3)3 氧化加成制备的 mer-iRhH[SiHPh2(SAr)(PMe3)3]会发生硫醇配体向配位 Si 原子的转移，从而得到 fac-[RhH2SiPh2(SAr)}(PMe3)3]。
• Preparation and structures of hydrido (organosilyl) arenethiolatorhodium(III) complexes with PMe3 ligands. Irreversible and reversible oxidative addition of an SiH bond to thiolatorhodium (I) complexes
  作者：Kohtaro Osakada、Kouji Hataya、Takakazu Yamamoto

  DOI：10.1016/s0020-1693(97)05449-2

  日期：1997.6

  Thiolatorhodium(I) complexes, Rh(SAr)L-3 (Ar=Ph (1), C6H4-p-Me (2), C6H4-p-OMe (3); L = PMe3), react with HSi(OMe)(3) and with HSiCl3 to give hydrido(silyl)arenethiolatorhodium(III) complexes, RhH(SiX3)(SAr)L-3 (X=OMe, Cl). Crystallographic results of RhH[Si(OMe)(3)](SPh)L-3 as well as NMR spectra of the complexes show octahedral coordination around the Rh center with thiolato and silyl ligands at mutually trans positions and three PMe3 ligands at meridional coordination sites. Hydride(triphenylsilyl)arenethiolatorhodium(III) complexes, RhH(SiPh3)(SAr)L-3 (Ar=Ph, C6H4-p-Me), are obtained from reaction of Rh(SAr)L-3 with excess HSiPh3. The complexes undergo reductive elimination of HSiPh3 in benzene solution at room temperature to regenerate thiolatorhodium(I) complexes and HSiPh3. Thermodynamic parameters of the reaction, Rh(SC6H4-p-Me)L-3 + HSiPh3 = RhH(SiPh3)(SC6H4-p-Me)L-3, are determined as Delta H degrees=-61.7+/-0.7 kJ mol(-1), Delta S degrees=-227+/-15 J mol(-1) deg(-1) and Delta G degrees=5.9 kJ mol(-1) at 298 K. Crystallographic results of RhH(SiPh3)(SAr)L-3 show that the Rh-Si bonds are significantly longer than those of RhH[Si(OMe)(3)](SPh)L-3. Reaction of HSiEt3 with 1-3 does not give oxidative addition products at all. Diarylsilanes, H2SiPh2, H2Si(C6H4-p-Me)(2), H2Si(C6H4-m-Me)(2) and H2Si(C6H4-p-F)(2), react readily with Rh(SAr)L-3 to give the corresponding oxidative addition products, RhH(SiHAr'(2))(SAr)L-3, that do not undergo reductive elimination of diarylsilane in the solutions.