{Rh2(CO)2(F3CC=CHCF3)(dmpm)2}{BF4} | 141585-07-1

• 英文名称: {Rh2(CO)2(F3CC=CHCF3)(dmpm)2}{BF4}
• CAS: 141585-07-1
• 化学式: BF₄*C₁₆H₂₉F₆O₂P₄Rh₂
• 分子量: 783.906
• InChiKey: WWVGGANGUSEQTN-UHFFFAOYSA-N

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：

  {Rh2(CO)2(F3CC=CHCF3)(dmpm)2}{BF4} 在 CO 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 以67%的产率得到{Rh2(CO)3(F3CC=CHCF3)(μ-CO)(dmpm)2}{BF4}
  参考文献：
  名称：

  Unusual low-valent dirhodium complexes bridged by bis(dimethylphosphino)methane ligands

  摘要：

  The low-valent complex [Rh2(CO)3(dmpm)2] (1) (dmpm = Me2PCH2PMe2) is prepared by the reaction of trans-[RhCl(CO)(dmpm)]2 with aqueous NaOH and CO. Under a CO atmosphere 1 is in equilibrium with the labile tetracarbonyl species [Rh(CO)(mu-CO)(dmpm)]2 (2). The structure of 1 is believed to be unsymmetrical having a trans arrangement of diphosphine ligands at one metal and a cis arrangement at the other, and a mixed-valence Rh(1+)/Rh(1-) formulation, while 2 is symmetric having the bridging diphosphines cis at both metals, and a corresponding Rh(0)/Rh(0) formulation. Reduction of [Rh2Cl2-(CO)2(mu-RC=CR)(dmpm)2] (R = CO2Me, CF3) yields [Rh2(CO))2(mu-RC=CR)(dmpm)2] (3, 4), which can also be obtained by alkyne addition to 1. The alkyne ligands are apparently bound perpendicular to the Rh-Rh axes in both species. Protonation of 1 with HBF4.OEt2 yields [Rh2(CO)3(mu-H)(dmpm)2][BF4], and under carbon monoxide this yields [Rh2(CO)4(mu-H)(dmpm)2][BF4]. Protonation of 3 yields [Rh2(CO)2-(mu-DMAD)(mu-H)(dmpm)2][BF4], whereas protonation of 4 yields [Rh2(CO)2(CF3C=C(H)CF3)(dmpm)2] [BF4], which apparently has a sigma, pi-vinylic moiety. Reaction of this vinyl complex with CO gives [Rh2(CO)3-(CF3C=C(H)CF3)(mu-CO)(dmpm)2][BF4] in which the vinyl group is sigma-bound to only one metal.

  DOI：

  10.1021/om00044a014
• 作为产物：
  描述：

  四氟硼酸-二乙醚络合物 、 {Rh2(CO)2(μ-HFB)(dmpm)2} 以 甲苯 为溶剂， 生成 {Rh2(CO)2(F3CC=CHCF3)(dmpm)2}{BF4}
  参考文献：
  名称：

  Unusual low-valent dirhodium complexes bridged by bis(dimethylphosphino)methane ligands

  摘要：

  The low-valent complex [Rh2(CO)3(dmpm)2] (1) (dmpm = Me2PCH2PMe2) is prepared by the reaction of trans-[RhCl(CO)(dmpm)]2 with aqueous NaOH and CO. Under a CO atmosphere 1 is in equilibrium with the labile tetracarbonyl species [Rh(CO)(mu-CO)(dmpm)]2 (2). The structure of 1 is believed to be unsymmetrical having a trans arrangement of diphosphine ligands at one metal and a cis arrangement at the other, and a mixed-valence Rh(1+)/Rh(1-) formulation, while 2 is symmetric having the bridging diphosphines cis at both metals, and a corresponding Rh(0)/Rh(0) formulation. Reduction of [Rh2Cl2-(CO)2(mu-RC=CR)(dmpm)2] (R = CO2Me, CF3) yields [Rh2(CO))2(mu-RC=CR)(dmpm)2] (3, 4), which can also be obtained by alkyne addition to 1. The alkyne ligands are apparently bound perpendicular to the Rh-Rh axes in both species. Protonation of 1 with HBF4.OEt2 yields [Rh2(CO)3(mu-H)(dmpm)2][BF4], and under carbon monoxide this yields [Rh2(CO)4(mu-H)(dmpm)2][BF4]. Protonation of 3 yields [Rh2(CO)2-(mu-DMAD)(mu-H)(dmpm)2][BF4], whereas protonation of 4 yields [Rh2(CO)2(CF3C=C(H)CF3)(dmpm)2] [BF4], which apparently has a sigma, pi-vinylic moiety. Reaction of this vinyl complex with CO gives [Rh2(CO)3-(CF3C=C(H)CF3)(mu-CO)(dmpm)2][BF4] in which the vinyl group is sigma-bound to only one metal.

  DOI：

  10.1021/om00044a014