fac-Rh(H)2(SiClPh2)(PMe3)3 | 194282-06-9

• 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: fac-Rh(H)2(SiClPh2)(PMe3)3
• CAS: 194282-06-9
• 化学式: C₂₁H₃₉ClP₃RhSi
• 分子量: 550.906
• InChiKey: KVNORINVGUFOAG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.57
• 重原子数：
  27.0
• 可旋转键数：
  6.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为产物：
  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

文献信息

• RhPt heterobimetallic and diplatinum complexes with bridging silyl and silylene ligands
  作者：Makoto Tanabe、Kohtaro Osakada

  DOI：10.1016/s0020-1693(02)01572-4

  日期：2003.7

  Platinum complexes Pt(SiHAr2)2(PMe3)2 (Ar=C6H5, C6H4F-4) react with RhCl(PMe3)3 to afford RhPt heterobimetallic complexes with bridging diarylsilyl and hydrido ligands, (Me3P)(Ar2ClSi)Pt(μ-H)(μ-η2-HSiAr2)Rh(PMe3)3 (1a: Ar=C6H5, 1b: Ar=C6H4F-4). The reaction is accompanied by the formation of small amounts of fac-RhH2(SiClAr2)(PMe3)3 (2a: Ar=C6H5, 2b: Ar=C6H4F-4). X-ray crystallography of 1a shows

  铂配合物Pt（SiHAr 2）2（PMe 3）2（Ar = C 6 H 5，C 6 H 4 F-4）与RhCl（PMe 3）3反应，得到具有桥联二芳基甲硅烷基和氢化配体的RhPt杂双金属配合物，（ME 3 P）（AR 2 CLSI）的Pt（μ-H）（μ-η 2 -HSiAr 2）的Rh（PME 3）3（1A：氩= C 6 H ^ 5，1B：氩= C 6 H ^ 4F-4）。该反应伴随着少量的形成FAC -RhH 2（SiClAr 2）（PME 3）3（图2a：氩= C 6 H ^ 5，图2b：氩= C 6 H ^ 4 F-4）。1a的X射线晶体学显示在Pt周围呈方形平面配位，在Rh周围具有八面体配位。二芳基甲硅烷基配体通过SiPtσ键和RhHSi三中心双电子键（3c-2e键）不对称地桥接到两个金属中心。的1 H和31 p 1H NMR光谱表明，在NMR时间尺度上，氢化物和SiH氢与键合到Rh的PMe