[Rh2(I,I)(bis(bis(trifluoroethoxy)phosphino)methylamine)3Cl2] | 601501-94-4

• 英文名称: [Rh2(I,I)(bis(bis(trifluoroethoxy)phosphino)methylamine)3Cl2]
• CAS: 601501-94-4
• 化学式: C₂₇H₃₃Cl₂F₃₆N₃O₁₂P₆Rh₂
• 分子量: 1738.07
• InChiKey: ZTPQHCSPGPGVNG-UHFFFAOYSA-L

计算性质

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

反应信息

• 作为反应物：
  描述：

  异氰酸叔丁酯 、 [Rh2(I,I)(bis(bis(trifluoroethoxy)phosphino)methylamine)3Cl2] 以 二氯甲烷 为溶剂， 以99%的产率得到
  参考文献：
  名称：

  A Photocycle for Hydrogen Production from Two-Electron Mixed-Valence Complexes

  摘要：

  Dihydrides of the formula Rh2(II,II)(tfepma)(3)H2Cl2 (tfepma = (bis[bis(trifluoroethoxy)phosphinojmethylamine, MeN(P[OCH2CF3](2))(2)), have been prepared by the addition of H-2 to the two-electron mixed-valence complex, Rh-2(0.11)(tfepma)(3)Cl-2 (1). Three isomeric forms with hydrides in syn (2), anti (3), and cis (4) conformations have been characterized by X-ray diffraction. Photolysis of 2 results in prompt formation of a short-lived blue photoproduct (Am = 600 nm) and a stoichiometric quantity of H-2, as determined by Toepler pump and isotopic labeling experiments. The blue photoproduct was identified as a Rh2(1.1) complex resulting from the reductive elimination of H-2, as determined from the examination of bimetallic cores coordinated by tfepm (tfepm = (bis[bis(trifluoroethoxy)phosphino]methane, CH2(P[OCH2CF3](2))(2)), for which complexes of the formula M-2(1.1)(tfepM)(3)Cl-2 (5, M = Rh and 6, M = Ir) have been isolated. The d8(...)d8 dimer of 5 converts to Rh-2(0.11)(tfepm)(3)Cl2CN/Bu (8) upon the addition of 1 equiv of tert-butylisonitrile, a result of halogen migration and disproportionation of the valence symmetric core of 5, which is structurally compared to its two-electron mixed-valence analogue, Rh-2(0.11)(dfpma)(3)(Cl2CNBu)-Bu-/ (9) (dfpma = bis(difluorophosphino)-methylamine, MeN(PF2)(2)). The halogen migration is captured in lr(2)(1.1)(tfePM)(3)(mu-Cl)Cl (7), which is distinguished by the presence of a chloride that bridges the diiridium centers. Taken together, complexes 1-9 permit the construction of a complete photocycle for the photogeneration of H-2 by dirhodium dfpma complexes in homogeneous solutions of hydrohalic acids.

  DOI：

  10.1021/ja054371x
• 作为产物：
  描述：

  酰亚胺基二亚磷酸,甲基-,四(2,2,2-三氟乙基)酯 、 chloro(1,5-cyclooctadiene)rhodium(I) dimer 以 二氯甲烷 为溶剂， 以82%的产率得到[Rh2(I,I)(bis(bis(trifluoroethoxy)phosphino)methylamine)3Cl2]
  参考文献：
  名称：

  A Photocycle for Hydrogen Production from Two-Electron Mixed-Valence Complexes

  摘要：

  Dihydrides of the formula Rh2(II,II)(tfepma)(3)H2Cl2 (tfepma = (bis[bis(trifluoroethoxy)phosphinojmethylamine, MeN(P[OCH2CF3](2))(2)), have been prepared by the addition of H-2 to the two-electron mixed-valence complex, Rh-2(0.11)(tfepma)(3)Cl-2 (1). Three isomeric forms with hydrides in syn (2), anti (3), and cis (4) conformations have been characterized by X-ray diffraction. Photolysis of 2 results in prompt formation of a short-lived blue photoproduct (Am = 600 nm) and a stoichiometric quantity of H-2, as determined by Toepler pump and isotopic labeling experiments. The blue photoproduct was identified as a Rh2(1.1) complex resulting from the reductive elimination of H-2, as determined from the examination of bimetallic cores coordinated by tfepm (tfepm = (bis[bis(trifluoroethoxy)phosphino]methane, CH2(P[OCH2CF3](2))(2)), for which complexes of the formula M-2(1.1)(tfepM)(3)Cl-2 (5, M = Rh and 6, M = Ir) have been isolated. The d8(...)d8 dimer of 5 converts to Rh-2(0.11)(tfepm)(3)Cl2CN/Bu (8) upon the addition of 1 equiv of tert-butylisonitrile, a result of halogen migration and disproportionation of the valence symmetric core of 5, which is structurally compared to its two-electron mixed-valence analogue, Rh-2(0.11)(dfpma)(3)(Cl2CNBu)-Bu-/ (9) (dfpma = bis(difluorophosphino)-methylamine, MeN(PF2)(2)). The halogen migration is captured in lr(2)(1.1)(tfePM)(3)(mu-Cl)Cl (7), which is distinguished by the presence of a chloride that bridges the diiridium centers. Taken together, complexes 1-9 permit the construction of a complete photocycle for the photogeneration of H-2 by dirhodium dfpma complexes in homogeneous solutions of hydrohalic acids.

  DOI：

  10.1021/ja054371x