mer-RhCl(H)[SiH(C6H5)2] | 194281-99-7

• 英文名称: mer-RhCl(H)[SiH(C6H5)2]
• CAS: 194281-99-7
• 化学式: C₂₁H₃₉ClP₃RhSi
• 分子量: 550.906
• InChiKey: YJEVZNSBLJAGJN-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  mer-RhCl(H)[SiH(C6H5)2] 以 甲苯 为溶剂， 以36%的产率得到fac-Rh(H)2(SiClPh2)(PMe3)3
  参考文献：
  名称：

  Structure and Chemical Properties of Chlorohydrido(diarylsilyl)rhodium(III) Complexes, mer-RhCl(H)(SiHAr₂)(PMe₃)₃. Thermally Induced Chloro Transfer from Rhodium to Silicon in the Complexes and Silane Exchange

  摘要：

  Reactions of the diarylsilanes H2SiPh2, H2Si(C6H4Me-p)(2), H2Si(C6H4OMe-p)(2), H2Si(C6H4F-p)(2), and H2Si(C6H4CF3-P)(2) with [Rh(PMe3)(4)]Cl involve oxidative addition of an Si-H bond of the substrates to give mer-RhCl(H)[SiH(C6H4X-p)(2)](PMe3)(3) ( 1, X = H; 2, X = Me; 3, X = OMe; 4, X = F; 5, X = CF3). X-ray crystallography of 1, 3, 4, and 5 shows a distorted-octahedral coordination around the Rh center with three meridional PMe3 Ligands and with the chloro and diarylsilyl ligands at mutually trans positions. The Rh-Si bond distances of the complexes are in the range 2.311-2.319 Angstrom. Addition of H2Si(C6H4Me-p)(2) to a toluene solution of 1 results in partial conversion of the complex into 2 accompanied by liberation of H2SiPh2. The exchange of the diphenylsilyl ligand of 1 on addition of the other diarylsilanes proceeds reversibly at 10-50 degrees C with the thermodynamic parameters of the reactions 1 + H2Si(C6H4X-p)(2) = mer-RhCl(H)[SIH(C6H4X-p)(2)](PMe3)(3) + H2SiPh2 as Delta H degrees = 4.16 kJ mol(-1) and Delta S degrees = 8.2 J mol(-1) K-1 for X = Me, Delta H degrees = 6.51 kJ mol(-1) and Delta S degrees = 11.7 J mol(-1) K-1 for X = OMe, and Delta H degrees = -2.33 kJ mol(-1) and Delta S degrees = -5.3 J mol(-1) K-1 for X = F, respectively. Enthalpy of the reactions of 1 with H2Si(C6H4X-p)(2) (X = Me, OMe, and F) decreases with increase in the sigma(p) value of X. Heating a toluene solution of 1 at 50 degrees C and at 110 degrees C gives mixtures of fac-Rh(H)(2)(siClPh(2))(PMe3)(3) (6) and RhCl(H)(SiClPh2)(PMe3)(3) (7). The structure of 6 has been determined by X-ray crystallography, while 7 was characterized by comparison of the NMR (H-1, P-31{H-1}, C-13{H-1}, and Si-29{H-1}) peaks with those of the complex prepared independently from the reaction of HSiClPh2 with [Rh(PMe3)(4)]Cl.

  DOI：

  10.1021/om970391z
• 作为产物：
  描述：

  二苯基硅烷 、 以 苯 为溶剂， 以96%的产率得到mer-RhCl(H)[SiH(C6H5)2]
  参考文献：
  名称：

  Structure and Chemical Properties of Chlorohydrido(diarylsilyl)rhodium(III) Complexes, mer-RhCl(H)(SiHAr₂)(PMe₃)₃. Thermally Induced Chloro Transfer from Rhodium to Silicon in the Complexes and Silane Exchange

  摘要：

  Reactions of the diarylsilanes H2SiPh2, H2Si(C6H4Me-p)(2), H2Si(C6H4OMe-p)(2), H2Si(C6H4F-p)(2), and H2Si(C6H4CF3-P)(2) with [Rh(PMe3)(4)]Cl involve oxidative addition of an Si-H bond of the substrates to give mer-RhCl(H)[SiH(C6H4X-p)(2)](PMe3)(3) ( 1, X = H; 2, X = Me; 3, X = OMe; 4, X = F; 5, X = CF3). X-ray crystallography of 1, 3, 4, and 5 shows a distorted-octahedral coordination around the Rh center with three meridional PMe3 Ligands and with the chloro and diarylsilyl ligands at mutually trans positions. The Rh-Si bond distances of the complexes are in the range 2.311-2.319 Angstrom. Addition of H2Si(C6H4Me-p)(2) to a toluene solution of 1 results in partial conversion of the complex into 2 accompanied by liberation of H2SiPh2. The exchange of the diphenylsilyl ligand of 1 on addition of the other diarylsilanes proceeds reversibly at 10-50 degrees C with the thermodynamic parameters of the reactions 1 + H2Si(C6H4X-p)(2) = mer-RhCl(H)[SIH(C6H4X-p)(2)](PMe3)(3) + H2SiPh2 as Delta H degrees = 4.16 kJ mol(-1) and Delta S degrees = 8.2 J mol(-1) K-1 for X = Me, Delta H degrees = 6.51 kJ mol(-1) and Delta S degrees = 11.7 J mol(-1) K-1 for X = OMe, and Delta H degrees = -2.33 kJ mol(-1) and Delta S degrees = -5.3 J mol(-1) K-1 for X = F, respectively. Enthalpy of the reactions of 1 with H2Si(C6H4X-p)(2) (X = Me, OMe, and F) decreases with increase in the sigma(p) value of X. Heating a toluene solution of 1 at 50 degrees C and at 110 degrees C gives mixtures of fac-Rh(H)(2)(siClPh(2))(PMe3)(3) (6) and RhCl(H)(SiClPh2)(PMe3)(3) (7). The structure of 6 has been determined by X-ray crystallography, while 7 was characterized by comparison of the NMR (H-1, P-31{H-1}, C-13{H-1}, and Si-29{H-1}) peaks with those of the complex prepared independently from the reaction of HSiClPh2 with [Rh(PMe3)(4)]Cl.

  DOI：

  10.1021/om970391z