(5,7,12,14-tetramethyldibenzo[b,i][1,4,8,11]tetraazacyclotetradecinate(2-))V=NCH3 | 174715-52-7

• 英文名称: (5,7,12,14-tetramethyldibenzo[b,i][1,4,8,11]tetraazacyclotetradecinate(2-))V=NCH3
• CAS: 174715-52-7
• 化学式: C₂₃H₂₅N₅V
• 分子量: 422.427
• InChiKey: OWAPWOCNWMVJHW-JSOLNSDESA-N

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：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  (5,7,12,14-tetramethyldibenzo[b,i][1,4,8,11]tetraazacyclotetradecinate(2-))V=NCH3 、 六氟丙酮 以 二氯甲烷 为溶剂， 以95%的产率得到(5,7,12,14-tetramethyldibenzo[b,i][1,4,8,11]tetraazacyclotetradecinate(2-))V(OC(CF3)2NCH3)
  参考文献：
  名称：

  Spectroscopy, Molecular Structure, Electrochemistry, and Reactivity of Vanadium(IV,V) Imido Complexes of 5,7,12,14-Tetramethyldibenzo[b,i][1,4,8,11]tetraazacyclotetradecine

  摘要：

  The synthesis of new imidovanadium(IV) complexes containing the tetradendate dianionic 5,7,12,14-tetramethyldibenzo[b,i][1, ,4,8,11]tetraazacyclotetradecinato moiety (TMTAA(2-)) is reported. Stirring of either [(HTMTAA)VCl2]Cl or (TMTAA)VCl2 in solution with NH(2)R was used to prepare very moisture-sensitive, paramagnetic compounds of the type (TMTAA)V=NR (2, R = CH3, t-C4H9, C6H5. C6F5 and N(CH3)(2)) in high yields. Complexes 2 were characterized by EPR, IR, UV/vis, and mass spectroscopic techniques. CV measurements indicate a reversible le-oxidation to the corresponding diamagnetic vanadium(V) cations [(TMTAA)V=NR](+) (4). Complexes 4 were prepared in preparative scale by oxidation of2 with 1 equiv of [(C5H5)(2)Fe]SbF6 (3) and characterized by heteronuclear NMR, IR, and UV/vis spectroscopic methods. While the V=NR group in complexes 2 does not react with Cr(CO)(5) or Pt(P(C6H5)(3))(2) under complexation, cycloaddition of 2a with hexfluoracetone has been observed. This reactivity has been compared to (TMTAA)V=O (5), which is demonstrated to undergo addition and cycloaddition reactions with hexafluoracetone, hexfluorpropene oxide, sulfur trioxide and triflic anhydride (complexes 8a-d). Complex 4b (R = t-C4H9) has been crystallographically characterized and the results discussed with those of 5 and [(TMTAA)V=O]SbF6 (6).

  DOI：

  10.1021/ic9508381
• 作为产物：
  描述：

  [(5,7,12,14-tetramethyldibenzo[b,i][1,4,8,11]tetraazacyclotetradecinate(1-))VCl2]Cl 、 甲胺 以 1,2-二氯乙烷 为溶剂， 以84%的产率得到(5,7,12,14-tetramethyldibenzo[b,i][1,4,8,11]tetraazacyclotetradecinate(2-))V=NCH3
  参考文献：
  名称：

  Spectroscopy, Molecular Structure, Electrochemistry, and Reactivity of Vanadium(IV,V) Imido Complexes of 5,7,12,14-Tetramethyldibenzo[b,i][1,4,8,11]tetraazacyclotetradecine

  摘要：

  The synthesis of new imidovanadium(IV) complexes containing the tetradendate dianionic 5,7,12,14-tetramethyldibenzo[b,i][1, ,4,8,11]tetraazacyclotetradecinato moiety (TMTAA(2-)) is reported. Stirring of either [(HTMTAA)VCl2]Cl or (TMTAA)VCl2 in solution with NH(2)R was used to prepare very moisture-sensitive, paramagnetic compounds of the type (TMTAA)V=NR (2, R = CH3, t-C4H9, C6H5. C6F5 and N(CH3)(2)) in high yields. Complexes 2 were characterized by EPR, IR, UV/vis, and mass spectroscopic techniques. CV measurements indicate a reversible le-oxidation to the corresponding diamagnetic vanadium(V) cations [(TMTAA)V=NR](+) (4). Complexes 4 were prepared in preparative scale by oxidation of2 with 1 equiv of [(C5H5)(2)Fe]SbF6 (3) and characterized by heteronuclear NMR, IR, and UV/vis spectroscopic methods. While the V=NR group in complexes 2 does not react with Cr(CO)(5) or Pt(P(C6H5)(3))(2) under complexation, cycloaddition of 2a with hexfluoracetone has been observed. This reactivity has been compared to (TMTAA)V=O (5), which is demonstrated to undergo addition and cycloaddition reactions with hexafluoracetone, hexfluorpropene oxide, sulfur trioxide and triflic anhydride (complexes 8a-d). Complex 4b (R = t-C4H9) has been crystallographically characterized and the results discussed with those of 5 and [(TMTAA)V=O]SbF6 (6).

  DOI：

  10.1021/ic9508381