W2(O2CMe3)4 | 86728-84-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: W2(O2CMe3)4
• CAS: 86728-84-9
• 化学式: 4C₅H₉O₂*2W
• 分子量: 772.201
• InChiKey: DSGMYJRFSXZEKT-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  -0.22
• 重原子数：
  8.0
• 可旋转键数：
  0.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  40.13
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为产物：
  描述：

  、 三甲基乙酸酐 以 正己烷 为溶剂， 生成 W2(O2CMe3)4
  参考文献：
  名称：

  Ring-Opening of σ-Thienyl and σ-Furyl Ligands at Ditungsten (M⋮M) Centers

  摘要：

  A series of compounds of formula 1,2-M(2)(sigma-Th)(2)(NMe(2))(4), 1, has been prepared, where M = Mo and/or W and Th = 2-thienyl[2-Th], 3-thienyl[3-Th], 5-methyl-2-thienyl[2,5-MeTh], and 2-benzothienyl[2-BTh]. In hydrocarbon solvents-these compounds exist as a mixture of anti and gauche rotamers having a central CN(2)M=MN(2)C core. Addition of (t)BuOH or CF(3)Me(2)COH to hydrocarbon solutions of 1, where M = W, lead to ring-opened products, 2, when the thienyl ligand is attached via the 2-carbon position. No ring-opening occurs for 3-thienyl derivatives. W-2(OR)(5) (mu-CCH2CHCHS) (sigma-2-Th), 2, where one of the 2-thienyl rings has been opened, has been fully characterized and shown to be derived from a ring-opened mu-vinylidene intermediate W-2(O(t)Bu)(4)(mu-CCHCHCHS)(sigma-2-Tn). Rather interestingly, the compound W-2(sigma-2-Th)(NMe(2))(5) reacts with (t)BuOH to give only W-2(2-Th)(O(t)Bu)(5) and HNMe(2). Reactions between 1 and the less sterically demanding alcohols (PrOH)-Pr-i and (t)BuCH(2)OH lead to W-2(OR)(6) compounds with liberation of HNMe(2) and the sulfur containing hydrocarbon. Compound 1 (M = W, 2-Th) reacts with CO2 to give W-2(NMe(2))(2)(O-2(NMe(2))(2)(sigma 2-Th)(2), 3, while with pivalic anhydride W-2(O(2)C(t)Bu)(4) is formed via reductive elimination of the C-C coupled product 2,2'-bithiophene and (t)BuCONMe(2) (4 equiv). 1 (M = W, 2-Th) and CO yield a product formulated as W-2(NMe(2))(4)(mu-CCHCHCHS)(sigma-2-Th)(CO)(3) wherein one ring has opened to form a mu-vinylidene thiolate Ligand. Attempts to prepare 1,2-W(2)L(2)(NMe(2))(4) compounds are described where L = an eta(1)- nitrogen containing heterocycle but only for L = 2-methylindolyl was a compound successfully characterized, Reactions of these compounds with (t)BuOH gave W-2(O(t)Bu)(6) and LH (2 equiv). The compound W-2(sigma-2-FU)(2)(NMe(2))(4) was prepared and characterized (2-Fu = 2-furyl) and shown to undergo ring-opening in its reaction with (t)BuOH to give W-2(O(t)Bu)(5)(mu u-CCH2CHCHO) (sigma-2-Fu), 4, in an analogous manner to the 2-Th complex. The complexes 1 (M = W, 2-Th), 2, 3, and 4 have been characterized by single crystal X-ray studies. The results described herein are compared to other ring-opening reactions of S, N, and O organic heterocyclic compounds as models for the activation of S, N, and O containing fossil fuels in hydrodesulfurization (HDS), hydrodenitrogenation (HDN), and hydrodeoxygenation (HDO) processes. The cleavage of the C-X bonds at the (M=M)(6+) centers (M = Mo, W and X = S, N and O) is also compared with earlier cleavage reactions involving C=O, RC=N, R(2)C=O, and Ar2C=S compounds.

  DOI：

  10.1021/ja962978v

文献信息

• Schrock, Richard R.; Sturgeoff, Lynda G.; Sharp, Paul R., Inorganic Chemistry, 1983, vol. 22, # 20, p. 2801 - 2806
  作者：Schrock, Richard R.、Sturgeoff, Lynda G.、Sharp, Paul R.

  DOI：——

  日期：——