[Rh(III)(1,4,7-triazacyclononane)H(formate)](OTf) | 867142-83-4

• 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: [Rh(III)(1,4,7-triazacyclononane)H(formate)](OTf)
• 英文别名: [Rh(III)(tacn)(formate)H](OTf)
• CAS: 867142-83-4
• 化学式: CF₃O₃S*C₇H₁₇N₃O₂Rh
• 分子量: 427.207
• InChiKey: MCTANVQUSMBHGZ-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：

  [Rh(III)(1,4,7-triazacyclononane)H(formate)](OTf) 在 HCOONa 作用下， 以 水 为溶剂， 生成 [Rh(III)(1,4,7-triazacyclononane)(H)2(CO)](OTf)
  参考文献：
  名称：

  Aqueous Transformation of a Metal Diformate to a Metal Dihydride Carbonyl Complex Accompanied by H₂ Evolution from the Formato Ligands

  摘要：

  The rhodium diformate complex [Rh-III(tacn)(HCOO)(2)](OTf) (2, tacn = 1,4,7-triazacyclononane, OTf- = CF3SO3-) reacts with HCOONa at pH 6-7 at 80 degrees C in water to form a rhodium dihydride CO complex, [Rh-III(tacn)(H)(2)(CO)](OTf) (5), with H-2 evolution from the formato ligands of 2. This is the first example of H-2 evolution from hydrogen atoms of formato ligands of a metal diformate complex. Complex 2 was synthesized from the reaction of a rhodium aqua complex, [Rh-III(tacn)(H2O)(3)](OTf)(3) (1), with HCOONa in water. Recrystallization of 2 with HCOONa in water gave crystals of a rhodium triformate complex, [Rh-III(tacn)(HCOO)(3)] (3), whose structure was unequivocally determined by X-ray analysis. The key intermediate in the transformation from 2 to 5 is a rhodium hydride formate complex, [Rh-III(tacn)H(HCOO)](OTf) (4), which was obtained by heating of an aqueous solution of the rhodium diformate complex 2 with 10 equiv of dimethyl sulfoxide (DMSO) at pH 6-7 in water. Complex 4 was well characterized by isotopic labeling measurements of H-1 NMR, electrospray ionization mass spectrometry (ESI-MS), and GC.

  DOI：

  10.1021/om0504147
• 作为产物：
  描述：

  [Rh(III)(1,4,7-triazacyclononane)(H2O)3](OTf)3 以 水 、 二甲基亚砜 为溶剂， 生成 [Rh(III)(1,4,7-triazacyclononane)H(formate)](OTf)
  参考文献：
  名称：

  Aqueous Transformation of a Metal Diformate to a Metal Dihydride Carbonyl Complex Accompanied by H₂ Evolution from the Formato Ligands

  摘要：

  The rhodium diformate complex [Rh-III(tacn)(HCOO)(2)](OTf) (2, tacn = 1,4,7-triazacyclononane, OTf- = CF3SO3-) reacts with HCOONa at pH 6-7 at 80 degrees C in water to form a rhodium dihydride CO complex, [Rh-III(tacn)(H)(2)(CO)](OTf) (5), with H-2 evolution from the formato ligands of 2. This is the first example of H-2 evolution from hydrogen atoms of formato ligands of a metal diformate complex. Complex 2 was synthesized from the reaction of a rhodium aqua complex, [Rh-III(tacn)(H2O)(3)](OTf)(3) (1), with HCOONa in water. Recrystallization of 2 with HCOONa in water gave crystals of a rhodium triformate complex, [Rh-III(tacn)(HCOO)(3)] (3), whose structure was unequivocally determined by X-ray analysis. The key intermediate in the transformation from 2 to 5 is a rhodium hydride formate complex, [Rh-III(tacn)H(HCOO)](OTf) (4), which was obtained by heating of an aqueous solution of the rhodium diformate complex 2 with 10 equiv of dimethyl sulfoxide (DMSO) at pH 6-7 in water. Complex 4 was well characterized by isotopic labeling measurements of H-1 NMR, electrospray ionization mass spectrometry (ESI-MS), and GC.

  DOI：

  10.1021/om0504147