mer-[RhH(SC6H4OMe-p)(SiH(C6H5)2)(PMe3)3] | 172613-01-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: mer-[RhH(SC6H4OMe-p)(SiH(C6H5)2)(PMe3)3]
• CAS: 172613-01-3
• 化学式: C₂₈H₄₆OP₃RhSSi
• 分子量: 654.651
• InChiKey: RQSPCYAGAVMISZ-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  6.48
• 重原子数：
  35.0
• 可旋转键数：
  9.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  9.23
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  mer-[RhH(SC6H4OMe-p)(SiH(C6H5)2)(PMe3)3] 以 not given 为溶剂， 生成 fac-[RhH2(Si(C6H5)2(SC6H4OMe-p))(PMe3)3]
  参考文献：
  名称：

  mer-[RhH(SAr)(SiHAr'2)(PMe3)3] tofac-[RhH2{SiAr'2(SAr)}(PMe3)3]的热异构化涉及硫醇基从Rh到Si的转移

  摘要：

  加热 mer-[RhH(SAr)(SiHAr'2)(PMe3)3] 的苯或甲苯溶液 (Ar = C6H5, C6H4Me-p, C6H4OMe-p; Ar' = C6H5, C6H4Me-p, C6H4F-p , C6H4CF3-p) 在 30-50 °C 下通过硫醇基从 Rh 转移到 Si 定量得到 fac-[RhH2{SiAr'2(SAr)}(PMe3)3]。fac-[RhH2{SiPh2(SPh)}(PMe3)3] 的 X 射线结构分析揭示了在面部配位位点与三个 PMe3 配体的八面体配位，而 1H NMR 光谱显示存在两个等效的氢化配体。其他Rh配合物通过核磁共振光谱法原位分离或表征。mer-[RhH(SC6H4Me-p)(SiHPh2)(PMe3)3]形成Rh配合物的反应服从一级动力学，动力学参数为：ΔG‡ = 98.6 kJ mol−1，ΔH‡ = 94.9 kJ mol −1，并且

  DOI：

  10.1246/bcsj.71.2853
• 作为产物：
  描述：

  [Rh(SC6H4OMe-p)(PMe3)3] 、 二苯基硅烷 以 正己烷 为溶剂， 生成 mer-[RhH(SC6H4OMe-p)(SiH(C6H5)2)(PMe3)3]
  参考文献：
  名称：

  Unique intramolecular exchange between H of SiHPh2 and SAr in [RhH(SiHPh2)(SAr)(PMe3)3]

  摘要：

  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-[RhH2{SiPh2(SAr)}(PMe3)3]。

  DOI：

  10.1039/c39950002315

文献信息

• 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.