| 206876-74-6

• CAS: 206876-74-6
• 化学式: C₄₆H₅₈ClO₄V
• 分子量: 761.359
• InChiKey: XGVOPVZGEICJAU-UHFFFAOYSA-K

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：

  在 I₂ 作用下， 以 四氢呋喃 为溶剂， 以70%的产率得到(O-methyl-p-tert-butyl-calix[4]arene)chlorovanadium(IV)
  参考文献：
  名称：

  The Chemistry of Vanadium−Carbon Bond Functionalities over an Oxo-Surface Defined by the Calix[4]arene Skeleton:  The Redox Relationship between Vanadium(III) and Vanadium(IV) Assisted by Carbon−Oxygen Bond Cleavage

  摘要：

  This report deals with the chemistry of V-C functionalities anchored to a quasi-planar O-4 matrix represented here by the [p-Bu-t-calix[4]-(OMe)(2)(O)(2)](2-) macrocycle. The starting material [p-Bu-t-calix[4]-(OMe)(2)(O)(2)V-Cl], 2, has been converted into the corresponding alkyl and aryl derivatives [p-Bu-t-calix[4]-(OMe)(2)(O)(2)V-R] (R = Me, 3; R = CH2Ph, 4; R = p-MeC6H4, 5) by conventional procedures. The structure of 5 reveals the self-assembling of the monomeric unit into a columnar arrangement with the p-tolyl substituent functioning as a guest moiety in a neighboring unit. Complexes 3-5 undergo migratory insertion reactions with CO and (BuNC)-N-t to the corresponding eta(2)-acyls [p-Bu-t-calix[4]-(OMe)(2)(O)(2)V(eta(2)-COR)] (R = Me, 6; R = CH2Ph, 7) and eta(2)-iminoacyls [p-Bu-t-calix[4]-(OMe)(2)(O)(2)V{eta(2)-C(NBut)R}] (R = Me, 8; R = CH2Ph, 9; R = p-MeC6H4, 10), the reaction with CO being strongly dependent on the R substituent. The structural model for the hexacoordinate intermediate leading to the inserted product is exemplified by the d(2) high-spin [p-Bu-t-calix[4]-(OMe)(2)(O)(2)V(Cl)(CNBut], 11, and proves the presence of four available orbitals at the metal for driving the reactivity in the [p-Bu-t-calix[4]-(OMe)(2)(O)(2)V] fragment. The bonding mode of the organic functionalities at the metal and the conversion of the alkyl substituent into the eta(2)-acyl have been inspected by extended Huckel calculations. The oxidative demethylation of 3 and 5 by a controlled amount of iodine opened an interesting synthetic route to the corresponding vanadium(IV) organometallic derivatives [p-Bu-t-calix[4]-(OMe)(O)(3)V-X] (X = Cl, 12; X = p-MeC6H4, 13). A structural report on 2, 5, and 9 is included.

  DOI：

  10.1021/om9800389
• 作为产物：
  描述：

  [VCl3(thf)3] 、 5,11,17,23-tetra-t-butyl-25,26,27,28-tetrahydroxycalix-4-arene 在 BuLi 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 以87%的产率得到
  参考文献：
  名称：

  The Chemistry of Vanadium−Carbon Bond Functionalities over an Oxo-Surface Defined by the Calix[4]arene Skeleton:  The Redox Relationship between Vanadium(III) and Vanadium(IV) Assisted by Carbon−Oxygen Bond Cleavage

  摘要：

  This report deals with the chemistry of V-C functionalities anchored to a quasi-planar O-4 matrix represented here by the [p-Bu-t-calix[4]-(OMe)(2)(O)(2)](2-) macrocycle. The starting material [p-Bu-t-calix[4]-(OMe)(2)(O)(2)V-Cl], 2, has been converted into the corresponding alkyl and aryl derivatives [p-Bu-t-calix[4]-(OMe)(2)(O)(2)V-R] (R = Me, 3; R = CH2Ph, 4; R = p-MeC6H4, 5) by conventional procedures. The structure of 5 reveals the self-assembling of the monomeric unit into a columnar arrangement with the p-tolyl substituent functioning as a guest moiety in a neighboring unit. Complexes 3-5 undergo migratory insertion reactions with CO and (BuNC)-N-t to the corresponding eta(2)-acyls [p-Bu-t-calix[4]-(OMe)(2)(O)(2)V(eta(2)-COR)] (R = Me, 6; R = CH2Ph, 7) and eta(2)-iminoacyls [p-Bu-t-calix[4]-(OMe)(2)(O)(2)V{eta(2)-C(NBut)R}] (R = Me, 8; R = CH2Ph, 9; R = p-MeC6H4, 10), the reaction with CO being strongly dependent on the R substituent. The structural model for the hexacoordinate intermediate leading to the inserted product is exemplified by the d(2) high-spin [p-Bu-t-calix[4]-(OMe)(2)(O)(2)V(Cl)(CNBut], 11, and proves the presence of four available orbitals at the metal for driving the reactivity in the [p-Bu-t-calix[4]-(OMe)(2)(O)(2)V] fragment. The bonding mode of the organic functionalities at the metal and the conversion of the alkyl substituent into the eta(2)-acyl have been inspected by extended Huckel calculations. The oxidative demethylation of 3 and 5 by a controlled amount of iodine opened an interesting synthetic route to the corresponding vanadium(IV) organometallic derivatives [p-Bu-t-calix[4]-(OMe)(O)(3)V-X] (X = Cl, 12; X = p-MeC6H4, 13). A structural report on 2, 5, and 9 is included.

  DOI：

  10.1021/om9800389