Ethylsulfanylethane;tetrachlorotungsten | 40354-86-7

• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 英文名称: Ethylsulfanylethane;tetrachlorotungsten
• CAS: 40354-86-7
• 化学式: C₈H₂₀Cl₄S₂W
• 分子量: 506.041
• InChiKey: HCRTUPBPJSGUCV-UHFFFAOYSA-J

计算性质

• 辛醇/水分配系数(LogP)：
  6.27
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  50.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  Ethylsulfanylethane;tetrachlorotungsten 、 (碘乙炔基)苯 以 四氯化碳 为溶剂， 以90%的产率得到
  参考文献：
  名称：

  Plate, Michael; Hofacker, Peter; Massa, Werner, Zeitschrift fur Naturforschung, B: Chemical Sciences, 1993, vol. 48, # 8, p. 1105 - 1111

  摘要：

  DOI：

文献信息

• Die Kristallstrukturen der Hexachlorometallate NH4[SbCl6], NH4[WCl6], [K(18-Krone-6)(CH2Cl2)]2[WCl6]·6CH2Cl2 und (PPh4)2[WCl6]·4CH3CN
  作者：C. Lau、A. Dietrich、M. Plate、P. Dierkes、B. Neumüller、S. Wocadlo、W. Massa、K. Harms、K. Dehnicke

  DOI：10.1002/zaac.200390078

  日期：2003.3

  (PPh4)2[WCl6]·4CH3CN kristallisiert monoklin in der Raumgruppe P21/c mit Z = 4. Auch diese Verbindung bildet zentrosymmetrische Ionentripel, in denen zusatzlich die Acetonitrilmolekule uber schwache C—H···Cl-Kontakte mit dem [WCl6]2—-Ion verbunden sind. Crystal Structures of the Hexachlorometalates NH4[SbCl6], NH4[WCl6], [K(18-crown-6)(CH2Cl2)]2[WCl6]·6CH2Cl2 and (PPh4)2[WCl6]·4CH3CN The crystal structures of the title

  借助X-射线单晶结构分析确定标题化合物的晶体结构。NH4 [SbCl6] 和 NH4 [WCl6] 在空间群 C2 / c 中彼此同型结晶，每个晶胞有四个分子式单元。NH4 + 离子位于双重旋转轴上，[MCl6] - 离子的金属原子占据反转中心。存在弱的离子间氢键。[K (18-Krone-6) (CH2Cl2)] 2 [WCl6] · 6CH2Cl2 在空间群 R3¯ / m 中正交结晶，Z = 3。该化合物形成中心对称离子三元组，其中钾离子与一个 WCl3 面配位每个。在与此相反的位置，CH2Cl2 分子的 Cl 原子配位，导致配位数为 10，与冠醚的 O 原子一起。(PPh4) 2 [WCl6] · 4CH3CN 在 Z = 4 的空间群 P21 / c 中单斜结晶。该化合物也形成中心对称离子三联体，其中乙腈分子也具有弱 C — H ... Cl 与 [WCl6 ] 2 - 离子相连。六氯金属盐的晶体结构
• N-heterocyclic carbene and cyclic (alkyl)(amino)carbene complexes of molybdenum(<scp>iv</scp>) and tungsten(<scp>iv</scp>)
  作者：Christian Luz、Eduard Glok、Günther Horrer、Udo Radius

  DOI：10.1039/d2dt03409c

  日期：——

  The synthesis and characterization of N-heterocyclic carbene (NHC) and cyclic (alkyl)(amino)carbene (cAAC) complexes of molybdenum(IV) and tungsten(IV) chloride is reported. Reaction of two equivalents of the NHCs IMes (1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene), IDipp (1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) and IiPrMe (1,3-diisopropyl-4,5-dimethylimidazolin-2-ylidene) with [MCl4(SEt)2]

  本文介绍了 NHC 和 cAACMe 稳定的 Mo(iv) 和 W(iv) 复合物的合成、表征和分子结构。
• Synthesis of Molybdenum and Tungsten Complexes That Contain Triamidoamine Ligands of the Type (C6F5NCH2CH2)3N and Activation of Dinitrogen by Molybdenum
  作者：Moshe Kol、Richard R. Schrock、Rhett Kempe、William M. Davis

  DOI：10.1021/ja00089a028

  日期：1994.5

  Three new ligands of the type (ArNHCH2CH2)(3)N (Ar = 3,5-bis(trifluoromethyl)phenyl, 2-(trifluoromethyl)phenyl, and pentafluorophenyl) have been prepared. Only Mo and W complexes containing the [(C6F5NCH2CH2)(3)N](3-) ([N3N](3-)) ligand were found to be stable. Stable complexes that have been prepared include Mo[N3N](NMe(2)), M[N3N]Cl(M = Mo or W), Mo[N3N](OTf) (M = Mo or W), [N3N]M=N (M = Mo or W), and [N3N]Mo=NMe}(OTf). An X-ray study of Mo[N3N]Cl showed it to be a monomeric distorted trigonal bipyramidal species having a pseudo-C-3 symmetry (space group P (1) over bar, a = 11.265(2) Angstrom, b = 11.371(2) Angstrom, c = 21.805(4) Angstrom, alpha = 82.40(1)degrees, beta = 79.07(1)degrees, gamma = 74.89(1)degrees, V = 2637.4 Angstrom(3), Z = 4, fw = 772.75, rho(calcd) = 1.946 g/cm(3), R = 0.032, R(W) = 0.034). Reduction of Mo[N3N](OTf) with 1 equiv of sodium amalgam yields a dinuclear bridging dinitrogen species, [N3N]Mo(mu N-2)Mo[N3N]. In the presence of 2 equiv of sodium amalgam in ether Mo[N3N](OTf) is reduced to [N3N]Mo(N-2)[Na(ether)(x)] (1 < x < 2). A more stable 15-crown-5 derivative can be prepared and more fully characterized. [N3N]Mo(mu-N-2)Mo[N3N] can be reduced to [N3N]Mo(N-2)[NaL(x)] by sodium amalgam under dinitrogen and the latter can be oxidized to the former by ferrocenium triflate or air. [N3N]Mo(N-2)[NaL(x)] reacts with Mo[N3N](OTf) to give [N3N]Mo(mu-N-2)Mo[N3N], with triisopropylsilyl chloride to give [N3N]MoN=NSi(i-Pr)(3), and with tributyltin chloride to give [N3N]MoN=NSn(Bu)(3). An X-ray study of [N3N]MoN=NSi(i-Pr)(3) (space group P2(1)/n, a 13.524(3) Angstrom, b = 18.016(4) Angstrom, c = 16.248(3) Angstrom, beta = 98.74(2)degrees, V = 3913(1) Angstrom(3), Z = 4, fw = 922.67, rho(calcd) = 1.566 g/cm(3), R = 0.069, R(W) = 0.072) showed it to be a trigonal bipyramidal complex containing a slightly bent diazenido ligand (Mo-N-alpha = 1.788(9) Angstrom, Mo-N-alpha-N-beta = 171.1(8)degrees, N-alpha-N-beta-Si = 154(1)degrees).
• Molybdenum and Tungsten Structural Differences are Dependent on <i>n</i>d<i>_z</i>_²/(<i>n</i> + 1)s Mixing: Comparisons of (silox)₃MX/R (M = Mo, W; silox = <i>^t</i>Bu₃SiO)
  作者：David S. Kuiper、Richard E. Douthwaite、Ana-Rita Mayol、Peter T. Wolczanski、Emil B. Lobkovsky、Thomas R. Cundari、Oanh P. Lam、Karsten Meyer

  DOI：10.1021/ic800139c

  日期：2008.8.1

  Treatment of trans-(Et2O)(2)MoCl4 with 2 or 3 equiv of Na(silox) (i.e., (NaOSiBu3)-Bu-t) afforded (Silox)(3)MoCl2 (1-Mo) or (silox)(3)MoCl (2-Mo). Purification of 2-Mo was accomplished via addition of PMe3 to precipitate (Silox)(3)CIMoPMe3 (2-MoPMe3), followed by thermolysis to remove phosphine. Use of MoCl3(THF)(3) with various amounts of Na(silox) produced (Silox)(2)ClMoMoCl(Silox)(2) (3-Mo). Alkylation of 2-Mo with MeMgBr or EtMgBr afforded (Silox)(3)MoR (R = Me, 2-MoMe; Et, 2-MoEt). 2-MoEt was also synthesized from C2H4 and (Silox)(3)MoH, which was prepared from 2-Mo and NaBEt3H. Thermolysis of WCl6 with (HOSiBu3)-Bu-t afforded (Silox)(2)WCl4 (4-W), and sequential treatment of 4-W with Na/Hg and Na(silox) provided (Silox)(3)WCl2 (1-W, tbp, X-ray), which was alternatively prepared from trans-(Et2S)(2) WCl4 and 3 equiv of Tl(silox). Na/Hg reduction of 1-W generated (silox)(3)WCl (2-W). Alkylation of 2-W with MeMgBr produced (Silox)(3)WMe (2-WMe), which dehydrogenated to (Silox)(3)WCH (6-W) with Delta H-double dagger = 14.9(9) kcal/ mol and Delta S-double dagger = -26(2) eu. Magnetism and structural studies revealed that 2-Mo and 2-MoEt have triplet ground states (GS) and distorted trigonal monopyramid (tmp) and tmp structures, respectively. In contrast, 2-W and 2-WMe possess squashed-T-d (distorted square planar) structures, and the former has a singlet GS. Quantum mechanics/ molecular mechanics studies of the S = 0 and S = 1 states for full models of 2-Mo, 2-MoEt, 2-W and 2-WMe corroborate the experimental findings and are consistent with the greater nd(z)(2)/(n + 1)s mixing in the third-row transition-metal species being the dominant feature in determining the structural disparity between molybdenum and tungsten.
• Listemann, Mark L.; Schrock, Richard R.; Dewan, John C., Inorganic Chemistry, 1988, vol. 27, # 2, p. 264 - 271
  作者：Listemann, Mark L.、Schrock, Richard R.、Dewan, John C.、Kolodziej, Richard M.

  DOI：——

  日期：——