{WCl4(thf)2} | 34445-14-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧唑烯
• 英文名称: {WCl4(thf)2}
• 英文别名: WCl4(THF)2；oxolane;tetrachlorotungsten
• CAS: 34445-14-2
• 化学式: C₈H₁₆Cl₄O₂W
• 分子量: 469.876
• InChiKey: GEEOGAJSWXZOST-UHFFFAOYSA-J

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：

  {WCl4(thf)2} 、 1,2-双(二甲基瞵)乙烷 在 sodium naphthalenide 作用下， 以 四氢呋喃 为溶剂， 以35%的产率得到trans-bis{1,2-bis(dimethylphosphino)ethane}dichlorotungsten(II)
  参考文献：
  名称：

  双[1,2-双（二甲基膦基）乙烷]二氯钨（II）及其反应。双[1,2-双（二甲基膦基）乙烷]四氯钨（V）六氯锑酸酯（V）和双{双[1,2-双（二甲基膦基乙烷）]四氢铝氢化钼（II）}的X射线晶体结构

  摘要：

  在1，2-双（二甲基膦基）乙烷（DMPE）存在下，在四氢呋喃中用萘钠还原WCl 4（THF）2得到反式-WCl 2（DMPE）2。此复合物与NaBPh的相互作用4在MeCN给出[WCL（η 2 -MeCN）（DMPE）2 ] BPH 4并用的SbCl 5钨（V）配合物[WCL 4（DMPE）2 ]的SbCl 6。后者的X射线晶体结构显示阳离子具有十二面体几何结构并带有赤道氯原子。反式-MCl 2（DMPE）的相互作用用LiAlH 4的2（M ＝ Mo和W）得到氢化铝氢化物[MH（AlH 4）（DMPE）2 ] 2，并且已经确定了钼化合物的X射线晶体结构。钨化合物的甲醇分解得到WH 4（DMPE）2。

  DOI：

  10.1016/s0277-5387(00)83618-9
• 作为产物：
  描述：

  四氢呋喃 、 六氯化钨 在 1-甲基-3,6-双(三甲基硅基)环己-1,4-二烯 作用下， 反应 1.0h， 以99%的产率得到{WCl4(thf)2}
  参考文献：
  名称：

  Salt-Free Reducing Reagent of Bis(trimethylsilyl)cyclohexadiene Mediates Multielectron Reduction of Chloride Complexes of W(VI) and W(IV)

  摘要：

  We developed a salt-free reduction of WCl6 using 1-methyl-3,6-bis(trimethylsilyl)-1,4-cyclohexadiene (MBTCD) in toluene to give a low-valent trinulcear tungsten complex involving W(II) and W(III) centers, while in the presence of redox active ligands such as alpha-diketone and alpha-diimine the same reduction produced W(IV) complexes with the corresponding redox-active ligands, (alpha-diketone)WCl4 and (alpha-diimine)WCl4. A W(VI) complex with two alpha-diketone ligands, (alpha-diketone)(2)WCl2, was found to be synthetically equivalent to low-valent W(IV) species that trapped azopyridine to give (alpha-diketone)WCl2(azopyridine).

  DOI：

  10.1021/ja401589a

文献信息

• Phosphorescent fac-Bis(triarylisocyanide) W(0) and Mo(0) Complexes
  作者：Mengwei Yue、Jiang He、Chao Zou、Xiaoyong Chang、Wei Lu

  DOI：10.1021/acs.inorgchem.3c03557

  日期：2024.2.19

  transfer (MLCT) transitions in nature. These complexes exhibited a reversible M+/0 redox couple at −0.70 and −0.63 V vs Fc+/0 for the W(0) complexes and −0.86 and −0.67 V for the Mo(0) complexes. The excited-state reduction potentials were hence estimated to be −2.91 and −2.74 V vs Fc+/0 for the W(0) complexes and −3.10 and −2.81 V vs Fc+/0 for the Mo(0) complexes, indicating that they are potentially strong

  合成了含有具有大取代基的双(三芳基异氰)配体的均配W(0)和Mo(0)配合物并进行了光谱表征。晶体学测定的结构表明，这些配合物呈沙漏状，三齿配体与金属中心采用面配位模式。这些配合物在流体溶液和固态中发光。通常在 298 K 的甲苯中，两个 W(0) 配合物在 591 nm（0.83 μs 和 0.35）和 628 nm（1.04 μs 和 0.39）处显示发射最大值（寿命和量子产率），类似地，两个 Mo( 0) 复合物在 575 nm（0.54 μs 和 0.15）和 617 nm（0.56 μs 和 0.23）处显示。 DFT和TDDFT计算表明W(0)和Mo(0)配合物的低能吸收带可能是自然界中金属到配体的电荷转移(MLCT)跃迁。这些配合物在W(0)配合物的-0.70和-0.63 V vs Fc +/0以及Mo(0)配合物的-0.86和-0.67 V处表现出可逆的M +/0氧化还原电对。因此，W(0)
• Bespoke Photoreductants: Tungsten Arylisocyanides
  作者：Wesley Sattler、Lawrence M. Henling、Jay R. Winkler、Harry B. Gray

  DOI：10.1021/ja510973h

  日期：2015.1.28

  Modular syntheses of oligoarylisocyanide ligands that are derivatives of 2,6-diisopropylphenyl isocyanide (CNdipp) have been developed; tungsten complexes incorporating these oligoarylisocyanide ligands exhibit intense metal-to-ligand charge-transfer visible absorptions that are red-shifted and more intense than those of the parent W(CNdipp)6 complex. Additionally, these W(CNAr)6 complexes have enhanced excited-state properties, including longer lifetimes and very high quantum yields. The decay kinetics of electronically excited W(CNAr)6 complexes (*W(CNAr)6) show solvent dependences; faster decay is observed in higher dielectric solvents. *W(CNAr)6 lifetimes are temperature dependent, suggestive of a strong coupling nonradiative decay mechanism that promotes repopulation of the ground state. Notably, *W(CNAr)6 complexes are exceptionally strong reductants: [W(CNAr)6](+)/*W(CNAr)6 potentials are more negative than -2.7 V vs [Cp2Fe](+)/Cp2Fe.
• Blower, Philip J.; Dilworth, Jonathan R.; Hutchinson, John, Journal of the Chemical Society, Dalton Transactions, 1985, p. 2639 - 2646
  作者：Blower, Philip J.、Dilworth, Jonathan R.、Hutchinson, John、Nicholson, Terry、Zubieta, Jon A.

  DOI：——

  日期：——
• Preparation and structure of the first ansa-molybdenocene and tungstenocene derivatives. Reaction of [O(SiMe2C5H4)2]MoH2 with methyl methacrylate to probe the olefin attacking site
  作者：Takaya Mise、Mami Maeda、Takayuki Nakajima、Kimiko Kobayashi、Isao Shimizu、Yasuhiro Yamamoto、Yasuo Wakatsuki

  DOI：10.1016/0022-328x(94)80116-9

  日期：1994.6

  Bridged-bis(cyclopentadienyl) molybdenum and tungsten dihydrides and their derivatives have been synthesized for the first time. [(1,1,3,3-Tetramethyldisiloxane-1,3-diyl)bis(eta5-cyclopentadienyl)]molybdenum dihydride (1a) and tungsten dihydride (1b) were prepared by sodium borohydride reduction of [O(SiMe2C5H4)2]MCl2 (2a: M = Mo, 2b: M = W) which was obtained by the reaction of disodium 1,1,3,3-tetramethyl-1,3-bis(cyclopentadienyl)disiloxane with MCl4(thf)2 (M = Mo, W). The dichlorides 2 reacted with ZnMe2 and NaSEt to afford [O(SiMe2C5H4)2]MMe2 (3a: M = Mo, 3b: M = W) and [O(SiMe2C5H4)2]M(SEt)2 (4a: M = Mo, 4b: M = W), respectively. Photolysis of lb in benzene gave [O(SiMe2C5H4)2]WH(C6H5) (5b). An X-ray crystal analysis of 3a has proved that the bridging chain blocks one of the side positions of the complex, the siloxy unit being present at one side of the Me-Mo-Me bisector. Consistent with side position attack by olefins, the reaction rate of la with methyl methacrylate was found to be nearly one half that of the parent CP2MoH2 (6a).
• Reduction of tungsten(VI) and molybdenum(V) by allyltrimethylsilane and cyclopentene. Simple high yield syntheses of MoCl4(OEt2)2, MoCl4(dme), WCl4(thf)2, WCl4(dme) and WOCl3(thf)2
  作者：Christina Persson、Carlaxel Andersson

  DOI：10.1016/s0020-1693(00)81663-1

  日期：1993.1

  Convenient high yield methods to prepare MoCl4(OEt2)2, MoCl4(dme), WCl4(thf)2, WCl4(dme) and WOCl3(thf)2 by reduction Of MOCl5 and WCl6, with olefins such as allyltrimethylsilane or cyclopentene are presented.