hexa(p-chlorophenoxy)tungsten | 4576-25-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: hexa(p-chlorophenoxy)tungsten
• 英文别名: (p-ClC6H4O)6W；Wolfram-hexa-<4-chlor-phenolat>；Wolfram-hexa-(4-chlor-phenolat)
• CAS: 4576-25-4
• 化学式: C₃₆H₂₄Cl₆O₆W
• 分子量: 949.151
• InChiKey: DAMCQBUYIAEQCW-UHFFFAOYSA-H

计算性质

• 辛醇/水分配系数(LogP)：
  13.1
• 重原子数：
  49.0
• 可旋转键数：
  12.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  55.38
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  氢化钾 、 hexa(p-chlorophenoxy)tungsten 在 Raney nickel 作用下， 以 乙醚 、 乙醇 为溶剂， 以61%的产率得到potassium hexa(p-chlorophenoxy)tungstate
  参考文献：
  名称：

  Syntheses and electrochemistry of (p-XC6H4O)6W (1-X, X=H, CH3, OCH3, Cl, Br, OH, OCH2Ph) and (p-XC6H4O)5W(OC6H4OH) (X=H, CH3, OCH3, Cl, Br): an approach to electrocatalytic CH bond activation

  摘要：

  Alcoholysis of W(OMe)(6) afforded (p-PhCH2OC6H4O)(6)W (1-OCH2Ph), which could be hydrogenated (10% Pd/C, 1 atm H-2) to prepare (p-HOC6H4O)(6)W (1-OH). Related alcoholyses of WCl6 with HOC6H4-p-X provided the hexaphenoxides (p-XC6H4O)(6)W (1-X, X = H, CH3, OCH3, Cl, Br) through minor modifications of literature procedures. Acid catalyzed treatment of 1-X with p-HOC6H4OCH2Ph provided a mixture of substitution products (p-XC6H4O)(6-x)W(OC6H4OCH2Ph), (x = 1, 5-X) that could be hydrogenated (10% Pd/C, 1 atm H-2) to a mixture of hydroxylated products. Chromatography permitted isolation of (p-XC6H4O)(5)W(OC6H4OH) (6-X, X = H, 19%; Me, 29%; OCH3, 19%; Cl, 12%; Br, 11%) in modest yields. Hexaphenoxides 1-X and 6-X manifested two electrochemical reduction waves whose positions were a function of para-substituent. When oxidized, 6-X and 1-OH were proposed to behave as W(V)quinone mimics, albeit at potentials capable of oxidizing hydrocarbons as shown via a thermochemical cycle. If the proposed transients (p-XC6H4O)(5)W(OC6H4O) (7-X) were generated, degradation was apparently competitive with CH bond activation. The structure of oligomeric {K[(p-ClC6H4O)(6)W]}(infinity) (8-Cl) is addressed, and comments on the nature of radical CH bond activation in this and related systems are presented. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2004.08.006
• 作为产物：
  描述：

  potassium hexa(p-chlorophenoxy)tungstate 在 Me₃SiCl 作用下， 以 not given 为溶剂， 生成 hexa(p-chlorophenoxy)tungsten
  参考文献：
  名称：

  Syntheses and electrochemistry of (p-XC6H4O)6W (1-X, X=H, CH3, OCH3, Cl, Br, OH, OCH2Ph) and (p-XC6H4O)5W(OC6H4OH) (X=H, CH3, OCH3, Cl, Br): an approach to electrocatalytic CH bond activation

  摘要：

  Alcoholysis of W(OMe)(6) afforded (p-PhCH2OC6H4O)(6)W (1-OCH2Ph), which could be hydrogenated (10% Pd/C, 1 atm H-2) to prepare (p-HOC6H4O)(6)W (1-OH). Related alcoholyses of WCl6 with HOC6H4-p-X provided the hexaphenoxides (p-XC6H4O)(6)W (1-X, X = H, CH3, OCH3, Cl, Br) through minor modifications of literature procedures. Acid catalyzed treatment of 1-X with p-HOC6H4OCH2Ph provided a mixture of substitution products (p-XC6H4O)(6-x)W(OC6H4OCH2Ph), (x = 1, 5-X) that could be hydrogenated (10% Pd/C, 1 atm H-2) to a mixture of hydroxylated products. Chromatography permitted isolation of (p-XC6H4O)(5)W(OC6H4OH) (6-X, X = H, 19%; Me, 29%; OCH3, 19%; Cl, 12%; Br, 11%) in modest yields. Hexaphenoxides 1-X and 6-X manifested two electrochemical reduction waves whose positions were a function of para-substituent. When oxidized, 6-X and 1-OH were proposed to behave as W(V)quinone mimics, albeit at potentials capable of oxidizing hydrocarbons as shown via a thermochemical cycle. If the proposed transients (p-XC6H4O)(5)W(OC6H4O) (7-X) were generated, degradation was apparently competitive with CH bond activation. The structure of oligomeric {K[(p-ClC6H4O)(6)W]}(infinity) (8-Cl) is addressed, and comments on the nature of radical CH bond activation in this and related systems are presented. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2004.08.006

文献信息

• Reactions of tris (1,2-ethanediolato)tungsten (VI) with phenyl acetates. X-ray structures of three products
  作者：Ari Lehtonen、Reijo Sillanpaa

  DOI：10.1016/s0277-5387(98)00281-2

  日期：1998.12

  Abstract Tungsten (VI) complex [W(eg)3] (eg=ethanediolate dianion) reacts with phenyl acetates leading to the displacement of one or three diolato ligands. Two types of phenoxides, [W(O–C6H4R-4)6] (R=H, Me, Cl) and [W(eg)2 (OC6H3R2′-2,6)2] (R′=Me, i Pr) are formed, depending on the nature of phenyl group. The X-ray crystal structure determinations of [W(OC6H5)6], [W(eg)2 (OC6H3Me2-2,6)2] and [W(eg)2

  摘要钨（VI）配合物[W（eg）3]（例如乙二醇二价阴离子）与乙酸苯酯反应，导致一或三个二醇基配体的置换。两种酚盐，[W（O–C6H4R-4）6]（R = H，Me，Cl）和[W（eg）2（OC6H3R2'-2,6）2]（R'= Me，i Pr取决于苯基的性质形成）。[W（OC6H5）6]，[W（eg）2（OC6H3Me2-2,6）2]和[W（eg）2（OC6H3i Pr2-2,6）2]的X射线晶体结构测定证实了化合物的性质。