(O-methyl-p-tert-butyl-calix[4]arene)chlorovanadium(IV) | 206876-84-8

• 英文名称: (O-methyl-p-tert-butyl-calix[4]arene)chlorovanadium(IV)
• 英文别名: VCl(Mecalix)
• CAS: 206876-84-8
• 化学式: C₄₅H₅₅ClO₄V
• 分子量: 746.324
• InChiKey: ZUCXTAJHAPHERX-UHFFFAOYSA-J

计算性质

• 辛醇/水分配系数(LogP)：
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• 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：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  (O-methyl-p-tert-butyl-calix[4]arene)chlorovanadium(IV) 、 sodium triphenylsilanolate 以 四氢呋喃 为溶剂， 以74.1%的产率得到(O-methyl-p-tert-butyl-calix[4]arene)triphenylsiloxyvanadium(IV)
  参考文献：
  名称：

  Vanadium calixarene complexes as molecular models for supported vanadia

  摘要：

  Reaction of dimethylated tert-butyl calix[4]arene, H(2)A(Me2), with O=VCl2(thf)(2) unexpectedly led to the isolation of Cl-V(IV)A(Me), 2, whose crystal structure was determined. Hence, one of the MeO-C bonds present in H(2)A(Me2) has been cleaved and one equivalent of HCl eliminated leaving three phenolate and one phenolether function to coordinate at the V centre. 2 smoothly reacts with O-2 to give O=V(V)A(Me), B, i.e. the chloride ligand has been replaced by a terminal oxo ligand with concomitant oxidation of the vanadium atom to the oxidation state +5. B crystallises isostructurally with 2; crystallisation of a mixture of 2 and B even leads to crystals that contain both compounds beside each other. However, when B was co-crystallised together with H(2)A(Me2), from acetonitrile a different structure with a partial cone conformation was obtained. The mechanism by which B is formed from 2 is discussed. To obtain information concerning the fate of the chloride ligand in 2, a derivative, Ph3SiO-V(IV)A(Me), 3, has been synthesised and investigated with respect to its behaviour in the presence of O-2: it reacts the same way as 2. (c) 2006 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molcata.2006.02.045
• 作为产物：
  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

文献信息

• Calix[4]arene supported group 5 imido complexes
  作者：Simon Dürr、Bettina Bechlars、Udo Radius

  DOI：10.1016/j.ica.2006.06.029

  日期：2006.10

  reaction of imidoyl chlorides [V(NR)Cl 3 ] (R = Ph 1 , Tol 2 , t Bu 3 ) and calix[4]arene methyl ether H 3 Mecalix unexpectedly leads to the formation of the structurally characterized vanadium (IV) complex [VCl(Mecalix)] ( 4 ). Calix[4]arene methyl ether stabilized imido complexes of the type [V(NR)(Mecalix)] (R = Ph 7 , Tol 8 , t Bu 9 ) were afforded from the reaction of [V(NR)Cl 3 ] (R = Ph 1 , Tol 2

  摘要亚氨酰氯[V（NR）Cl 3]（R = Ph 1，Tol 2，t Bu 3）与杯[4]芳烃甲基醚H 3 Mecalix的反应出乎意料地导致了结构上具有特征的钒（IV ）复数[VCl（Mecalix）]（4）。由[V（NR）Cl 3]的反应得到[V（NR）（Mecalix）]类型的杯[4]芳烃甲基醚稳定的亚氨基配合物（R ＝ Ph 7，Tol 8，t Bu 9）（ R = Ph 1，Tol 2，t Bu 3）和杯[4]芳烃醚的三（锂）或三（钠）盐。锂盐[Li 3（Mecalix）} 2]（5）是固态的二聚体，其中两个单体三价阴离子通过锂阳离子桥接。亚氨基复合物[M（NR）（Mecalix）]（M = Nb：R = t Bu，12，R = Tol 13，R = Mes 14，R = Dipp 15; M = Ta：R = t Bu 16，R = Tol 17）（Tol = 4-C 6 H