[CH2=C(C5H4N)O-κ2-N,O]2Zr(NEt2)2 | 724425-47-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: [CH2=C(C5H4N)O-κ2-N,O]2Zr(NEt2)2
• 英文别名: Diethylazanide;1-pyridin-2-ylethenolate;zirconium(4+)
• CAS: 724425-47-2
• 化学式: C₂₂H₃₂N₄O₂Zr
• 分子量: 475.746
• InChiKey: HAFLFBNPPUTHEO-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  3.62
• 重原子数：
  29
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  73.9
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  [CH2=C(C5H4N)O-κ2-N,O]2Zr(NEt2)2 、 三甲基铝 以 苯 为溶剂， 以43%的产率得到[CH2=C(C5H4N)(OAlMe3)-κ2-N,O]AlMe2
  参考文献：
  名称：

  Pyridineenolato and pyridineenamido complexes of zirconium, titanium and aluminum

  摘要：

  Deprotonation of 2-acetylpyridine with KH in THF afford a potassium enolate compound (2) which reacts with Zr(NEt2)(2)Cl-2(THF)(2) and Ti(NMe2)(2)Cl-2 to yield [CH2 = C(C5H4N)O-kappa(2)N,O](2)M(NR2)(2) (M = Zr, R = Et, 3; M = Ti, R = Me, 4) in 84% and 76% yield, respectively. Deprotonation of imines derived from 2-acetylpyridine, (2,6-Me2C6H3)N = C(C5H4N)(CH3) (5) and (2,6-iPr(2)C(6)H(3))N = C(C5H4N)(CH3) (6), affords potassium enamides, K[(2,6-Me2C6H3)N-C(C5H4N)( = CH2)] (7) and K[(2,6-iPr(2)C(6)H(3))N-(C5H4N)( = CH2)] (8). Reactions of the potassium salt 7 with Zr(NEt2)(2)Cl-2(THF)(2) and Ti(NMe2)(2)Cl-2 afford pyridineenamido complexes, [(2,6-Me2C6H3)NC(C5H4N)( = CH2)-kappa(2)N,N](2)M(NR2)(2) (M = Zr, R = Et, 9; M = Ti, R = Me, 10). Reaction of 8 with Zr(NEt2)(2)Cl-2(THF)(2) affords [(2,6-iPr(2)C(6)H(3))NC(C5H4N)( = CH2)](2)Zr(NEt2)(2) (11) but the reaction of 8 with Ti(NMe2)(2)Cl-2 yields [(2,6-iPrC(6)H(3))NC(C5H4N)( = CH2)]TiCl(NMe2)(2) (12). Addition of excess AlMe3 to 3 or 4 results in transmetallation of Zr or Ti to Al to afford an aluminum enolate complex, [CH2 = C(C5H4N)(OAlMe3)-kappa(2)N,O]AlMe2 (13). Addition of AlMe3 to 12 results in the formation of a transmetallated complex, [(2,6-iPr(2)C(6)H(3))NC(C5H4N)( = CH2)]AlMe2 (14). The solid structures of 4, 11, 13 and 14 were determined by X-ray crystallography. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2004.03.009
• 作为产物：
  描述：

  bis(diethylamido)-dichloridozirconium(lV)-bis(tetrahydrofurane) 、 Potassium;1-pyridin-2-ylethanone 以 四氢呋喃 为溶剂， 以84%的产率得到[CH2=C(C5H4N)O-κ2-N,O]2Zr(NEt2)2
  参考文献：
  名称：

  Pyridineenolato and pyridineenamido complexes of zirconium, titanium and aluminum

  摘要：

  Deprotonation of 2-acetylpyridine with KH in THF afford a potassium enolate compound (2) which reacts with Zr(NEt2)(2)Cl-2(THF)(2) and Ti(NMe2)(2)Cl-2 to yield [CH2 = C(C5H4N)O-kappa(2)N,O](2)M(NR2)(2) (M = Zr, R = Et, 3; M = Ti, R = Me, 4) in 84% and 76% yield, respectively. Deprotonation of imines derived from 2-acetylpyridine, (2,6-Me2C6H3)N = C(C5H4N)(CH3) (5) and (2,6-iPr(2)C(6)H(3))N = C(C5H4N)(CH3) (6), affords potassium enamides, K[(2,6-Me2C6H3)N-C(C5H4N)( = CH2)] (7) and K[(2,6-iPr(2)C(6)H(3))N-(C5H4N)( = CH2)] (8). Reactions of the potassium salt 7 with Zr(NEt2)(2)Cl-2(THF)(2) and Ti(NMe2)(2)Cl-2 afford pyridineenamido complexes, [(2,6-Me2C6H3)NC(C5H4N)( = CH2)-kappa(2)N,N](2)M(NR2)(2) (M = Zr, R = Et, 9; M = Ti, R = Me, 10). Reaction of 8 with Zr(NEt2)(2)Cl-2(THF)(2) affords [(2,6-iPr(2)C(6)H(3))NC(C5H4N)( = CH2)](2)Zr(NEt2)(2) (11) but the reaction of 8 with Ti(NMe2)(2)Cl-2 yields [(2,6-iPrC(6)H(3))NC(C5H4N)( = CH2)]TiCl(NMe2)(2) (12). Addition of excess AlMe3 to 3 or 4 results in transmetallation of Zr or Ti to Al to afford an aluminum enolate complex, [CH2 = C(C5H4N)(OAlMe3)-kappa(2)N,O]AlMe2 (13). Addition of AlMe3 to 12 results in the formation of a transmetallated complex, [(2,6-iPr(2)C(6)H(3))NC(C5H4N)( = CH2)]AlMe2 (14). The solid structures of 4, 11, 13 and 14 were determined by X-ray crystallography. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2004.03.009