WCl4(Me2S)2 | 53922-82-0

• 分子结构分类: 有机化合物 - 有机磷化合物
• 英文名称: WCl4(Me2S)2
• CAS: 53922-82-0
• 化学式: C₄H₁₂Cl₄S₂W
• 分子量: 449.933
• InChiKey: SCESOSUCDVEOFT-UHFFFAOYSA-J

计算性质

• 辛醇/水分配系数(LogP)：
  4.71
• 重原子数：
  11.0
• 可旋转键数：
  2.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  WCl4(Me2S)2 、 三乙基(硅烷-d) 生成 trichlorotungsten(III)bis(μ-dimethyl sulfide)(μ-D)(dimethylsulfide)dichlorotungsten(III)
  参考文献：
  名称：

  The synthesis and characterization of µ-hydrido-bis-(µ-sulphide)-ditungsten(III) complexes: the X-ray crystal structure of [HPPh₃][Cl₃W(µ-H)(µ-Me₂S)₂WCl₃]

  摘要：

  WCl4(Me2S)2 与 Et3SiH 反应生成 Cl3W(µ-H)(µ-Me2S)2WCl2(Me2S)，由此可制备阴离子 [Cl3W(µ-H)(µ-Me2S)2WCl3]-；对[HPPh3][Cl3W(µ-H)-(µ-Me2S)2WCl3]的单晶 X 射线衍射研究表明，这些配合物具有共面生物八面体框架，具有长度为 2-410(7)埃的正式 W-W 三键。

  DOI：

  10.1039/c39810001286

文献信息

• Studies of confacial bioctahedral tungsten complexes containing metal-to-metal bonds: synthesis, reactions, and nuclear magnetic resonance studies of W₂Cl₄(μ-SR)₂(μ-S)L₂ (R = alkyl; L = monodentate ligand)
  作者：Vlkram D. Patel、P. Michael Boorman

  DOI：10.1139/v82-197

  日期：1982.6.1

  A series of new binuclear tungsten(IV) complexes, W₂Cl₄(μ-SR)₂(μ-S)L₂ (R = Me, Et, ⁱBu, CH₂Ph; L = Me₂S or THT), is readily synthesized from the metathetical reaction of WCl₄L₂ with 1 mol-equiv. of alkylthiotrimethylsilane (Me₃Si(SR)). These complexes react with stronger nucleophiles (Ph₃P, MeCN, C₅H₅N, Cl⁻) under ambient conditions to yield simple disubstituted products. Reaction of W₂Cl₄(μ-SEt)₂(μ-S)(SMe₂)₂ with PhCH₂X (X = Cl, Br) yields [Me₂SCH₂Ph]₂[W₂Cl₄(μ-SEt)₂(μ-S)X₂], whilst with stronger alkylating agents, MeSO₃F or Et₃OBF₄, intractable residues result.The series of homologous complexes has been studied by ¹H and ¹³C nmr spectroscopy. When R = Me, two stable configurational isomers are present in solution, whilst only a single isomer exists for more bulky R groups. Trends in the ¹H nmr chemical shifts of the methylene and methyl protons of the SEt groups in the complexes W₂Cl₄(μ-SEt)₂(μ-S)L₂ allow absolute assignment of the resonances to two magnetically inequivalent thiolato groups.

  一系列新的二核钨（IV）配合物W2Cl4（μ-SR）2（μ-S）L2（其中R = Me，Et，iBu，CH2Ph; L = Me2S或THT），可以通过WCl4L2与1摩尔当量的烷基硫基三甲基硅烷（Me3Si（SR））的交换反应轻松合成。这些配合物在常温下与更强的亲核试剂（Ph3P，MeCN，C5H5N，Cl-）反应，生成简单的二取代产物。W2Cl4（μ-SEt）2（μ-S）（SMe2）2与PhCH2X（X = Cl，Br）的反应生成[Me2SCH2Ph]2[W2Cl4（μ-SEt）2（μ-S）X2]，而使用更强的烷基化试剂MeSO3F或Et3OBF4会产生难以处理的残留物。这一系列同系列配合物已通过1H和13C NMR光谱进行研究。当R = Me时，溶液中存在两个稳定的构型异构体，而对于更大的R基团，只存在单个异构体。配合物W2Cl4（μ-SEt）2（μ-S）L2中SEt基团的甲基和亚甲基质子的1H NMR化学位移趋势允许将共振归属于两个磁性不等效的硫醇基团。
• Confacial bioctahedral complexes of tungsten(IV) containing tungsten-to-tungsten bonds: X-ray crystal structures of di-μ-ethanethiolato-μ-sulfidobis[dichloro(dimethyl sulfide)-tungsten(IV) (W—W)] and tetraphenylphosphonium di-μ-ethane thiolato-μ-sulfido- bis[trichlorotungstate(IV) (W—W)]
  作者：P. Michael Boorman、Penelope W. Codding、K. Ann Kerr、Kelly J. Moynihan、Vikram D. Patel

  DOI：10.1139/v82-196

  日期：1982.6.1

  The complex (Me₂S)Cl₂W(μ-S)(μ-SEt)₂WCl₂(Me₂S), 1, has been prepared by reaction of [WCl₄(Me₂S)₂] with 1 mol-equiv. of SiMe₃(SEt) in CH₂Cl₂ solution. A single-crystal X-ray diffraction study shows that the molecule has a confacial bioctahedral structure with a W—W bond length of 2.526(2) Å. The structure was solved by heavy atom methods and refined to R = 0.061 and R_w = 0.061 for 2715 reflections with I ≥ 3σ(1). Crystals of 1 are triclinic, space group [Formula: see text], with a = 9.661(1), b = 10.695(1), c = 13.253(4) Å, α = 61.84(2), β = 66.98(2), and γ = 66.44(1)°, Z = 2.Reaction of 1with 2 mol-equiv. of Ph₄PCl in CH₂Cl₂ solution yields (Ph₄P)₂[Cl₃W(μ-S)(μ-SEt)₂WCl₃], 2. Crystals of 2 are triclinic, space group [Formula: see text], with a = 10.153(1), b = 13.043(1), c = 21.876(3) Å, α = 95.16(1), β = 96.48(2), and γ = 108.90(1)°, Z = 2. The structure was refined to R = 0.041, R_w = 0.048 for 2384 reflections with I ≥ 3σ(1); 2 also has a confacial bioctahedral structure with a W—W bond length of 2.522(1) Å.

  复合物(Me₂S)Cl₂W(μ-S)(μ-SEt)₂WCl₂(Me₂S)，1，是通过在CH₂Cl₂溶液中反应[WCl₄(Me₂S)₂]和1摩尔当量的SiMe₃(SEt)制备的。单晶X射线衍射研究表明，该分子具有一个面向的双八面体结构，W-W键长为2.526(2) Å。该结构是通过重原子方法解决的，并对I≥3σ(1)的2715个反射进行了R = 0.061和R_w = 0.061的精修。1的晶体是三斜晶系，空间群[公式：见文本]，a = 9.661(1) Å，b = 10.695(1) Å，c = 13.253(4) Å，α = 61.84(2)°，β = 66.98(2)°和γ = 66.44(1)°，Z = 2。在CH₂Cl₂溶液中，1和2摩尔当量的Ph₄PCl反应产生(Ph₄P)₂[Cl₃W(μ-S)(μ-SEt)₂WCl₃]，2。2的晶体是三斜晶系，空间群[公式：见文本]，a = 10.153(1) Å，b = 13.043(1) Å，c = 21.876(3) Å，α = 95.16(1)°，β = 96.48(2)°和γ = 108.90(1)°，Z = 2。该结构经过2384个反射的精修，其中I≥3σ(1)，R = 0.041，R_w = 0.048；2也具有一个面向的双八面体结构，W-W键长为2.522(1) Å。
• Synthesis, X-ray crystal structure, and electronic structure of a trinuclear WCu2 cluster containing a hexathiolato tungsten(IV) core
  作者：Joanne M. Ball、P. Michael Boorman、James F. Fait、Tom Ziegler

  DOI：10.1039/c39890000722

  日期：——

  In the new compound (PPh3)Cu(µ-Sptol)3W(µ-Sptol)3Cu(PPh3), (ptol = 4-methylphenyl, p-tolyl), the tungsten is homoleptically ligated by six thiolate ligands, and co-ordinates to two copper(I) atoms in a biconfacial octahedral/tetrahedral geometry; density functional calculations of an idealized model show that the major component of the bonding is transfer of charge from S to Cu, with a smaller contribution

  在新的化合物（PPh 3）Cu（µ-Sptol）3 W（µ-Sptol）3 Cu（PPh 3）（ptol = 4-甲基苯基，对甲苯基）中，钨被六个硫醇盐配体同质连接，并与双面八面体/四面体几何中的两个铜（I）原子配位；理想化模型的密度泛函计算表明，键合的主要成分是电荷从S转移到Cu，而金属-金属键合相互作用的贡献较小。
• Michael Boorman; Moynihan, Kelly J.; Patel, Vikram D., Inorganic Chemistry, 1985, vol. 24, # 19, p. 2989 - 2997
  作者：Michael Boorman、Moynihan, Kelly J.、Patel, Vikram D.、Richardson, John F.

  DOI：——

  日期：——
• Patel, Vikram D.; Boorman, P. Michael; Kerr, K. Ann, Inorganic Chemistry, 1982, vol. 21, # 4, p. 1383 - 1387
  作者：Patel, Vikram D.、Boorman, P. Michael、Kerr, K. Ann、Moynihan, Kelly J.

  DOI：——

  日期：——