| 200207-30-3

• CAS: 200207-30-3
• 化学式: C₄₅H₄₂ClN₂P₃RhS*Cl
• 分子量: 909.641
• InChiKey: INBPYZZPGAWLBX-UHFFFAOYSA-K

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 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：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为产物：
  描述：

  三氯[1,1,1-三(二苯基膦基甲基)乙烷]铑 、 2-巯基嘧啶 在 NaOMe 作用下， 以 甲醇 为溶剂， 以74%的产率得到
  参考文献：
  名称：

  Arm-off reactions of the tripodal polyphosphane MeC(CH2PPh2)3 in octahedral rhodium(III) complexes of heterocyclic thioamides

  摘要：

  Arm-off kappa(3)P-->kappa(2)P processes of the tripodal polyphosphane MeC(CH2PPh2)(3) have been studied for reactions of [RhCl3(triphos)] (1a) and [Rh(MeCN)(3)(triphos)](CF3SO3)(3) (1b) with chelating bi- and tridentate anionic ligands. Treatment of 1a with the heterocyclic thioamides Hmpym (2-mercaptopyrimidine) or Hmtz (2-mercapto-1-methylimidazole) affords the complexes [RhCl(mpym)(triphos)]Cl (2) and [RhCl(mtz)(triphos)]Cl (3), which are stereochemically rigid in CDCl3 solution at room temperature. In contrast, the presence of two broad unstructured resonances at 10.6 and 13.5 ppm in the P-31 NMR spectrum of [Rh(mpym)(MeCN)(triphos)](CF3SO3)(2) (4) in CD3CN solution at 25 degrees C indicates a rapid exchange of the phosphorus environments, for which either an acetonitrile or a triphos arm-off dissociation can be postulated. Such a kappa(3)P-->kappa(2)P mechanism is required for the formation of [Rh(mpym)(2)(triphos)](CF3SO3) (5), [Rh(mbt)(2)(triphosO)](CF3SO3) (6), [Rh(mmim)(2)(triphosO)](CF3SO3) (7) and [RhH(HBpz(3))(triphosO)](CF3SO3) (8) on treatment of 1b with the required ligand (Hmbt = 2-mercaptobenzothiazole; Hmmim = 2-mercapto-1-methylimidazole) at a stoichiometric ratio. Rapid oxidation of the liberated dangling triphos arm to the phosphane oxide O=P(Ph-2)CH2C(CH3)(CH2PPh2)(2) (triphosO) is typical for kappa(2)P coordinated Rh(III) complexes. (C) 1998 Elsevier Science S.A.

  DOI：

  10.1016/s0020-1693(97)05549-7