cis-{Rh(4,4'-(t-Bu)2bipyridyl)2Cl2}Cl | 116996-77-1

• 英文名称: cis-{Rh(4,4'-(t-Bu)2bipyridyl)2Cl2}Cl
• 英文别名: [(4,4′-di-tert-butyl-2,2′-bipyridyl)₂RhCl₂]Cl；[(^tbpy)2Rh(Cl)2]Cl
• CAS: 116996-77-1
• 化学式: C₃₆H₄₈Cl₂N₄Rh*Cl
• 分子量: 746.068
• InChiKey: ZNCLSTHELUEKDR-UHFFFAOYSA-K

计算性质

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

• 作为反应物：
  描述：

  cis-{Rh(4,4'-(t-Bu)2bipyridyl)2Cl2}Cl 在 cesiumhydroxide monohydrate 、 三氟乙酸 作用下， 以 四氢呋喃 、 乙腈 为溶剂， 20.0~70.0 ℃ 、377.13 kPa 条件下， 反应 17.5h， 生成 [(4,4′-di-tert-butyl-2,2′-bipyridyl)₂RhCl₂][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

文献信息

• Synthesis of Rh ^III Anilido, Hydroxide, and Methoxide Complexes
  作者：Samantha A. Burgess、Tamara Bolaño、T. Brent Gunnoe、Michal Sabat、William H. Myers

  DOI：10.1002/ejic.201403147

  日期：2015.2

  The octahedral RhIII complexes [(tbpy)2Rh(XH)2][OTf]3 (tbpy = 4,4′-di-tert-butyl-2,2′-bipyridyl; X = NHPh or OH; OTf = trifluoromethanesulfonate), [(tbpy)2Rh(X)2][OTf] (X = NHPh or OH), [(tbpy)2Rh(NHPh)(NH2Ph)][OTf]2, [(tbpy)2Rh(Me)(NH2Ph)][OTf][BAr′4] (BAr′4 = tetrakis[(3,5-bis-trifluoromethyl)phenyl]borate), [(tbpy)2Rh(Me)(NHPh)][BAr′4], [(tbpy)2Rh(OMe)(Cl)]Cl, and [(bpy)Rh(X)2][PF6] (bpy = 2,2′-bipyridyl;

  八面体 RhIII 配合物 [(tbpy)2Rh(XH)2][OTf]3（tbpy = 4,4'-二叔丁基-2,2'-联吡啶；X = NHPh 或 OH；OTf = 三氟甲磺酸盐）， [(tbpy)2Rh(X)2][OTf] (X = NHPh 或 OH), [(tbpy)2Rh(NHPh)(NH2Ph)][OTf]2, [(tbpy)2Rh(Me)(NH2Ph)] [OTf][BAr'4] (BAr'4 = 四[(3,5-双-三氟甲基)苯基]硼酸盐), [(tbpy)2Rh(Me)(NHPh)][BAr'4], [(tbpy )2Rh(OMe)(Cl)]Cl 和 [(bpy)Rh(X)2][PF6]（bpy = 2,2'-联吡啶；X = OH，OMe）已被合成并通过 1H、13C 表征1H} 和 19F NMR 光谱、元素分析或高分辨率质谱以及某些配合物的单晶 X 射线衍射。[(tbp