[(4,4′-di-tert-butyl-2,2′-bipyridyl)₂Rh(hydride)(trifluoroacetate)][trifluoromethanesulfonate] | 1609035-95-1

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: [(4,4′-di-tert-butyl-2,2′-bipyridyl)₂Rh(hydride)(trifluoroacetate)][trifluoromethanesulfonate]
• CAS: 1609035-95-1
• 化学式: CF₃O₃S*C₃₈H₄₉F₃N₄O₂Rh
• 分子量: 902.804
• InChiKey: VCLSIJRMBCRPPY-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：

  [(4,4′-di-tert-butyl-2,2′-bipyridyl)₂Rh(hydride)(trifluoroacetate)][trifluoromethanesulfonate] 、 氢气 以 氘代四氢呋喃 、 二氯甲烷 为溶剂， 70.0 ℃ 、273.7 kPa 条件下， 反应 144.0h， 以91%的产率得到[(4,4′-di-tert-butyl-2,2′-bipyridyl)₂Rh(H)(Cl)][trifluoroacetate]
  参考文献：
  名称：

  1,2-Addition of Dihydrogen across Rhodium(III)–OMe Bonds

  摘要：

  The Rh(III) complexes [((t)bpy)(2)Rh(OMe)(L)]-[X] [X](n) ((t)bpy) = 4,4'-di-tert-butyl-2,2'-bipyridyl; L = MeOH, n = 2, X = OTf (OTf = trifluoromethanesulfonate), TFA (TFA = trifluoroacetate); L = TFA, n = 1, X = OTf) have been shown to activate dihydrogen via net 1,2-addition of the H H bond across the Rh-III-OMe bond. The bis(methoxide) complex [((t)bPY)(2)Rh(OMe)(2)][OTf] was synthesized by addition of CsOH center dot H2O in methanol to [((t)bPY)(2)Rh(OTf)(2)[OTf] in CH3CN. The addition of HTFA to [((t)bpy)(2)Rh(OMe)(2)][OTf] leads to the formation of [((t)bpy)(2)Rh(OMe)(MeOH)][OTf][TFA], which exists in equilibrium with [((t)bpy)(2)Rh(OMe)(TFA)][OTf]. The mixture of [((t)bpy)(2)Rh(OMe)(MeOH)] [OTf][TFA] and [((t)bpy)(2)Rh(OMe)(TFA)][OTf] activates dihyclrogen at 68 degrees C to give methanol and [((t)bpy)(2)Rh(H)(TFA)][OTf]. Studies indicate that the activation of dihydrogen has a first-order dependence on the Rh(III) methoxide complex and a dependence on hydrogen that is between zero and first order. Combined experimental and computational studies have led to a proposed mechanism for hydrogen activation by [((t)bpy)(2)Rh(OMe)(MeOH)][OTf][TFA] that involves dissociation of Me0H, coordination of hydrogen, and 1,2-addition of hydrogen across the Rh OMe bond. DFT calculations indicate that there is a substantial energy penalty for MeOH dissociation and a relatively flat energy surface for subsequent hydrogen coordination and activation.

  DOI：

  10.1021/ic500636m
• 作为产物：
  描述：

  4,4'-二叔丁基-2,2'-二吡啶 以 四氢呋喃 、 氘代丙酮 为溶剂， 反应 0.5h， 生成 [(4,4′-di-tert-butyl-2,2′-bipyridyl)₂Rh(hydride)(trifluoroacetate)][trifluoromethanesulfonate]
  参考文献：
  名称：

  1,2-Addition of Dihydrogen across Rhodium(III)–OMe Bonds

  摘要：

  The Rh(III) complexes [((t)bpy)(2)Rh(OMe)(L)]-[X] [X](n) ((t)bpy) = 4,4'-di-tert-butyl-2,2'-bipyridyl; L = MeOH, n = 2, X = OTf (OTf = trifluoromethanesulfonate), TFA (TFA = trifluoroacetate); L = TFA, n = 1, X = OTf) have been shown to activate dihydrogen via net 1,2-addition of the H H bond across the Rh-III-OMe bond. The bis(methoxide) complex [((t)bPY)(2)Rh(OMe)(2)][OTf] was synthesized by addition of CsOH center dot H2O in methanol to [((t)bPY)(2)Rh(OTf)(2)[OTf] in CH3CN. The addition of HTFA to [((t)bpy)(2)Rh(OMe)(2)][OTf] leads to the formation of [((t)bpy)(2)Rh(OMe)(MeOH)][OTf][TFA], which exists in equilibrium with [((t)bpy)(2)Rh(OMe)(TFA)][OTf]. The mixture of [((t)bpy)(2)Rh(OMe)(MeOH)] [OTf][TFA] and [((t)bpy)(2)Rh(OMe)(TFA)][OTf] activates dihyclrogen at 68 degrees C to give methanol and [((t)bpy)(2)Rh(H)(TFA)][OTf]. Studies indicate that the activation of dihydrogen has a first-order dependence on the Rh(III) methoxide complex and a dependence on hydrogen that is between zero and first order. Combined experimental and computational studies have led to a proposed mechanism for hydrogen activation by [((t)bpy)(2)Rh(OMe)(MeOH)][OTf][TFA] that involves dissociation of Me0H, coordination of hydrogen, and 1,2-addition of hydrogen across the Rh OMe bond. DFT calculations indicate that there is a substantial energy penalty for MeOH dissociation and a relatively flat energy surface for subsequent hydrogen coordination and activation.

  DOI：

  10.1021/ic500636m