[Cu(bis[(2-pyridyl)methyl]amine)Cl2][Cu(bis[(2-pyridyl)methyl]amine)(H2O)Cl][Cu(bis[(2-pyridyl)methyl]amine)Cl][CuCl4] | 745784-37-6

• 英文名称: [Cu(bis[(2-pyridyl)methyl]amine)Cl2][Cu(bis[(2-pyridyl)methyl]amine)(H2O)Cl][Cu(bis[(2-pyridyl)methyl]amine)Cl][CuCl4]
• CAS: 745784-37-6
• 化学式: C₁₂H₁₃ClCuN₃*C₁₂H₁₃Cl₂CuN₃*C₁₂H₁₅ClCuN₃O*Cl₄Cu
• 分子量: 1153.59
• InChiKey: BRSXYVLUAQZOJF-UHFFFAOYSA-F

反应信息

• 作为产物：
  描述：

  Boc-Leu-bis[(2-pyridyl)methyl]amine 、 copper(II) choride dihydrate 以 甲醇 为溶剂， 生成 [Cu(bis[(2-pyridyl)methyl]amine)Cl2][Cu(bis[(2-pyridyl)methyl]amine)(H2O)Cl][Cu(bis[(2-pyridyl)methyl]amine)Cl][CuCl4]
  参考文献：
  名称：

  The Activation of Tertiary Carboxamides in Metal Complexes: An Experimental and Theoretical Study on the Methanolysis of Acylated Bispicolylamine Copper(II) Complexes

  摘要：

  It is a well-established concept that the C-N bond cleavage of carboxamide functions is facilitated by the coordination of a metal ion to the carbonyl oxygen atom. In contrast, the alternative C-N bond activation by coordination of a neutral tertiary carboxamide nitrogen atom has not been studied. We present the first results on the effect of nitrogen pyramidalization in N-coordinated metal complexes on the methanolysis of tertiary carboxamide groups. An analysis of the reactions products obtained from the methanol cleavage of [(N-Acyl-bpa)Cu](2+) (bpa = N,N-bispicolylamine) complexes is presented together with experimental and high-level theoretically calculated structures. The strong effect of different anions on the amide pyramidalization and subsequent C-N-bond cleavage is evaluated. We show that dichloro complexes [(N-Acyl-bpa)CuCl2] have much less activated amide groups than the corresponding triflate species. They should therefore be less reactive. However, [(N-Acyl-bpa)CuCl2] complexes dissociate in solution to give cationic monochloro complexes [(N-Acyl-bpa)Cu(S)Cl](+) (S = solvent molecule). Theoretical calculations show that the amide pyramidalization in the monochloro complexes is equal to that in the corresponding CF3SO3- salts. Consequently, chloro and triflato complexes are cleaved with similar rates and efficiencies. Parallels to and differences in the reactivity of purely organic distorted amides are discussed.

  DOI：

  10.1021/ic0496774