bis(triphenylphosphane)(4,5-diazafluorenide)dihydridorhodium(III) | 1208005-92-8

• 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: bis(triphenylphosphane)(4,5-diazafluorenide)dihydridorhodium(III)
• CAS: 1208005-92-8
• 化学式: C₄₇H₃₉N₂P₂Rh
• 分子量: 796.693
• InChiKey: SEPBYOGAMKNHJG-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：

  二氧化碳 、 bis(triphenylphosphane)(4,5-diazafluorenide)dihydridorhodium(III) 以 甲苯 为溶剂， 以95%的产率得到
  参考文献：
  名称：

  Tuning the Reactivity of an Actor Ligand for Tandem CO₂and C–H Activations: From Spectator Metals to Metal-Free

  摘要：

  The 4,5-diazafluorenide ligand (L-) serves as an actor ligand in the formal insertion of CO2 into a C-H bond remote from the metal center. With the Ru(II) complex of L- as the starting point, Rh(III), Rh(I), and Cu(I) were used as spectator metal centers to tune the reactivity of the actor ligand toward CO2. In the case of Rh(III)-diazafluorenide a room temperature reversible activation of CO2 was observed, similar to the isoelectronic Ru(II) analogue. In the case of Rh(I)- and Cu(I)-diazafluorenide CO2 is trapped by the formation of dinuclear carboxylate complexes and diazafluorene (LH). The spectator metal center could even be replaced entirely with an organic group allowing for the first metal-free reversible tandem CO2 and C-H activation.

  DOI：

  10.1021/ja4073832
• 作为产物：
  描述：

  bis(triphenylphosphane)(4,5-diazafluorene)dihydridorhodium(III) chloride - dichloromethane (1/0.125) 在 NaH 作用下， 以 四氢呋喃 为溶剂， 以99%的产率得到bis(triphenylphosphane)(4,5-diazafluorenide)dihydridorhodium(III)
  参考文献：
  名称：

  铑 4,5-二氮杂芴衍生物的合成、结构和反应性

  摘要：

  四种铑4,5-二氮杂芴衍生物，[RhL(PPh3)2] (1), [Rh(H)2(LH)(PPh3)2]Cl (2), [Rh(H)2L(PPh3)2] (3) 和 [Rh(H)2(LH)(PPh3)2]OTf (4) 已经合成，并通过 NMR 光谱、元素分析和单晶 X 射线衍射进行了充分表征。当用氢气处理时，化合物1可以转化为3。用NaH处理化合物2可转化为3，用HCl水溶液处理3可实现逆反应。空气和湿气稳定的化合物 2 是多种烯烃加氢的活性催化剂，包括非末端烯烃；2 中的氯反离子似乎在催化系统中起作用。因此，化合物 4，即 2 的三氟甲磺酸酯类似物，对烯烃氢化反应无活性。（© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009）

  DOI：

  10.1002/ejic.200801195

文献信息

• Reaction of Dinuclear Rhodium 4,5-Diazafluorenyl-9-Carboxylate Complexes with H₂ and CO₂
  作者：Vincent T. Annibale、Datong Song

  DOI：10.1021/om500278a

  日期：2014.6.9

  The reactivity of the dinuclear Rh(I) 4,5-diazafluorenyl-9-carboxylate complex 4 with H-2 was explored in an attempt to reduce the trapped CO2-derived moiety. After overnight reaction with H2 the only observed species at room temperature by NMR spectroscopy was the decarboxylated 4,5-diazafluorenyl (L-) Rh(III) complex 1. A series of stepwise stoichiometric reactions with H2, NMR experiments at low temperatures, trapping experiments with added PPh3 or CO2, and C-13-labeling experiments were conducted in an attempt to identify the fates of the CO2-derived portion of 4 and the second Rh center.