hexa(p-methylphenoxy)tungsten | 4503-99-5

• 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-methylphenoxy)tungsten
• 英文别名: [W(OC6H4Me-4)6]；(p-MeC6H4O)6W；Wolfram-hexa-(4-methyl-phenolat)；Wolfram-hexa-(p-methyl-phenolat)
• CAS: 4503-99-5
• 化学式: C₄₂H₄₂O₆W
• 分子量: 826.642
• InChiKey: WZKQOYDURMXFDP-UHFFFAOYSA-H

计算性质

• 辛醇/水分配系数(LogP)：
  11.03
• 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：
  0.14
• 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：

  4-苄氧基苯酚 、 hexa(p-methylphenoxy)tungsten 在 catalyst: p-toluenesulfonic acid monohydrate 作用下， 以 氯苯 为溶剂， 生成 penta(p-methylphenoxy)(p-benzyloxyphenoxy)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
• 作为产物：
  描述：

  对甲酚 、 六氯化钨 以 氯苯 为溶剂， 以60%的产率得到hexa(p-methylphenoxy)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 monocyclopentadienyl complexes of molybdenum and tungsten with derivatives of phenols and pentafluorobenzeneselenol
  作者：Jack L. Davidson、Birgit Holz、Pascal C. Leverd、W. Edward Lindsell、Nigel J. Simpson

  DOI：10.1039/dt9940003527

  日期：——

  Photolysis of [Mo(CO)3(cp)}2] with Se2(C6F5)2 in toluene yields [Mo(SeC6F5)(CO)3(Cp)]8a, and the thermal reaction of [MoCl(CO)3(Cp)] with two equivalents of Tl(SeC6F5) in diethyl ether gives the thallium complex Tl[Mo(SeC6F5)2(CO)2(Cp)]9, via complex 8a isolated as a by-product. Reaction of [WBr3(CO)2(Cp)] with three equivalents of Tl(SeC6F5) produces [W(SeC6F5)3(CO)(Cp)]12, with [W(SeC6F5)(CO)3(Cp)]8b as

  的反应[WI 3（CO）2（CP）]（CP =η 5 -C 5 H ^ 5）用铊盐铊（OR）（R =芳基）在四氢呋喃没有产生简单的替换产品，而且，得到还原的物质[W （OC 6 F 5）（CO）3（CP）] 2，氧化物种[W（OC 6 H 4 Me- p）6 ]或tri三钨衍生物[Tl W（CO）3（CP）} 3 ] （当R = C 6 H 3 Pr i 2 2,6时）。复杂2是[WX（CO）3（CP）]类型的衍生物的罕见例子，其中X是与氧键合的配体。[Mo（CO）3（CP）} 2 ]与Se 2（C 6 F 5）2在甲苯中的光解产生[Mo（SeC 6 F 5）（CO）3（CP）] 8a和热反应[MoCl（CO）3（CP）]与二当量的Tl（SeC 6 F 5）在乙醚中的混合，得到via络合物Tl [Mo（SeC 6 F 5）2（CO）2（CP）] 9作为副产物分离出的复合物8a。[WBr
• 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。
• Beshouri, Sharon M.; Rothwell, Ian P., Inorganic Chemistry, 1986, vol. 25, # 12, p. 1962 - 1964
  作者：Beshouri, Sharon M.、Rothwell, Ian P.

  DOI：——

  日期：——
• Solid state and solution studies of tungsten(VI) oxotetraalkoxides
  作者：William Clegg、R. John Errington、Peter Kraxner、Carl Redshaw

  DOI：10.1039/dt9920001431

  日期：——

  Variable-temperature H-1 NMR studies of the oxoalkoxides, WO(OR)4 (R = Me, Et, Pr(i), or cyclo-C6H11), show these compounds to be dynamic in solution. For R = Me or Et, limiting spectra have been obtained which are consistent with alkoxide-bridged binuclear structures, and for R = Me or cyclo-C6H11, X-ray diffraction studies confirm that these structures are adopted in the solid state. The alkoxide bridges are asymmetric [R = Me, 2.032(7) and 2.242(12) angstrom (average); R = cyclo-C6H11, 2.044(4) and 2.250(4) angstrom] and coplanar with the terminal oxo groups, the longer W-OR bonds being trans to the short W = O bonds. Tungsten-183 NMR chemical shifts of the compounds with R = Me, Et, cyclo-C6H11, Bu(t) or C6H3Pr(i)2-2,6 are very sensitive to the nature of the alkoxo ligand, and range from delta -62.9 for [WO(OMe)4}2] to -493.6 for mononuclear [WO(OC6H3Pr(i)2-2,6)4]. Possible solution equilibria are discussed in the light of these NMR results. An attempt to prepare [WO(OC6H4Me-4)4] yielded [W(OC6H4Me-4)6], and an X-ray crystal structure determination showed this compound to be octahedral with an average W-O bond length of 1.895(9) angstrom.