tris(benzene-1,2-dithiolato)tungsten(VI) | 10507-73-0

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: tris(benzene-1,2-dithiolato)tungsten(VI)
• 英文别名: tris(1,2-benzenethiolato)tungsten；W^VI(benzene-1,2-dithiolate)3；[W(benzene-1,2-dithiolate)3]
• CAS: 10507-73-0；212210-81-6
• 化学式: C₁₈H₁₂S₆W
• 分子量: 604.539
• InChiKey: MKQRSTANWQEOCB-UHFFFAOYSA-H

计算性质

• 辛醇/水分配系数(LogP)：
  8.4
• 重原子数：
  25.0
• 可旋转键数：
  0.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  tris(benzene-1,2-dithiolato)tungsten(VI) 以 四氢呋喃 、 甲醇 、 乙醚 、 二氯甲烷 为溶剂， 生成 {W(S2C6H4)(MeSC6H4)2}
  参考文献：
  名称：

  Transition metal complexes with sulphur ligands. Part 67. A novel type of reaction: nucleophilic alkylation of thiolato ligands by carbanions via intramolecular electron transfer. Alkylation and reduction of [W(S2C6H4)3] by lithium alkyls

  摘要：

  The reaction of [W(S2C6H4)3] 1 with LiMe depends on the concentration of the latter and yields either the anionic tungsten(iv) complex [NR4][W(S2C6H4)2(MeSC6H4S)] (R = Me, 2a; or Et, 2b) or the anionic tungsten(v) complex [NMe4][W(S2C6H4)3] 3b. This novel type of reaction demonstrates the reactive versatility of transition-metal sulphur centres and is of importance for the understanding of trans-methylation reactions catalysed by oxidoreductases with sulphur-co-ordinated transition-metal centres, e.g. CO dehydrogenase. When 1 is treated with LiEt, LiCH2Bu(t) or LiPh only a reduction of 1 takes place yielding 3b. The reaction of complex 1 with 2 equivalents of LiBu(n) affords the dianionic tungsten(iv) complex [NMe4]2[W(S2C6H4)3] 4. The electrophilic alkylation of 4 by 2 equivalents of R3OBF4 (R = Me or Et) or of 2b by 1 equivalent of Me3OBF4 leads to the doubly alkylated complexes [W(S2C6H4)(RSC6H4S)2] (R = Me, 5a; or Et, 5b).

  DOI：

  10.1039/dt9910001733

文献信息

• Synthesis and X-ray Molecular Structure of [WVI(C6H4S2-1,2)3] Completing the Structural Characterization of the Series [W(C6H4S2-1,2)3]n (n = 0, 1, 2): Trigonal-Prismatic versus Octahedral Coordination in Tris(benzene-1,2-dithiolato) Complexes
  作者：HanVinh Huynh、Thomas Lügger、F. Ekkehardt Hahn

  DOI：10.1002/1099-0682(200211)2002:11<3007::aid-ejic3007>3.0.co;2-i

  日期：2002.11

  The tris(benzene-1,2-dithiolato) complex [WVI(C6H4S2-1,2)3] 1 was synthesized from [W(CH3)6] and C6H4(SH)2-1,2 in diethyl ether. Crystals of [WVI(C6H4S2-1,2)3] were obtained from a saturated dichloromethane solution at room temperature. The X-ray crystal structure analysis revealed that the tungsten atom in 1 is coordinated in an almost perfect trigonal-prismatic fashion with W−S distances between

  三（苯-1,2-二硫醇）络合物 [WVI(C6H4S2-1,2)3] 1 由 [W(CH3)6] 和 (SH)2-1,2 在乙醚中合成。[WVI( S2-1,2)3]晶体在室温下从饱和二氯甲烷溶液中获得。X 射线晶体结构分析表明，1 中的钨原子以几乎完美的三角棱镜方式配位，其 W-S 距离在 2.3724(14) A 和 2.3840(14) A 之间。
• The reduction of tris-dithiolene complexes of molybdenum(<scp>vi</scp>) and tungsten(<scp>vi</scp>) by hydroxide ion: kinetics and mechanism
  作者：Antonio Cervilla、Francisco Pérez-Plá、Elisa Llopis、María Piles

  DOI：10.1039/b402234c

  日期：——

  of molybdenum(VI) and tungsten(VI), (L = S2C6H4(2-), S2C6H3CH3(2-) and S2C2(CH3)2(2-); M = Mo or W) by tetrabutylammonium hydroxide in tetrahydrofuran-water solutions demonstrates that OH- is an effective reductant. Their reduction is fast, clean and quantitative. Depending upon both the molar ratio in which the reagents are mixed and the amount of water present, one- or two-electron reductions of these

  钼（VI）和钨（VI）（L = S2C6H4（2-），S2C6H3 （2-）和S2C2（CH3）2（2）的某些中性三-二硫代亚砜络合物[ML3]自发还原的动力学研究-）; M = Mo或W）在四氢呋喃水溶液中的四丁基氢氧化铵表明OH-是有效的还原剂。它们的减少是快速，清洁和定量的。取决于混合试剂的摩尔比和存在的水的量，观察到这些三-二硫代噻吩配合物的一电子或二电子还原。如果Bu4NOH以低浓度或/和高浓度的水存在，则仅观察到中性M（VI）配合物向单阴离子M（V）配合物的总转化。该反应的停止流动力学数据与速率定律一致：-d [ML3] / dt = d [ML3-] / dt = k [ML3] [Bu4NOH]。拟议的机制涉及OH-的亲核攻击，形成单阴离子七配位中间体[ML3OH]-，该中间体与另一分子[ML3]相互作用生成单阴离子配合物[ML3]-将氧从配位的OH-转移至水。过氧化氢
• Reduction of Tris(benzene-1,2-dithiolate)molybdenum(VI) by Water. A Functional Mo−Hydroxylase Analogue System
  作者：Antonio Cervilla、Francisco Pérez-Pla、Elisa Llopis、María Piles

  DOI：10.1021/ic0483242

  日期：2005.6.1

  MOVI(S2C6H4)(3) reacts cleanly and completely with H2O in THF to afford [H3O]+[Mo-V(S2C6H4)(3)](-). Kinetic data were fit by the rate equation -d[Mo-VI(S2C6H4)(3)]/dt = k[Mo-VI(S2C6H4)(3)]/[H3O+], which is consistent with a coupled electron-proton transfer mechanism involving a coordinated H2O molecule. The Mo-VI(S2C6H4)(3) reduction is accelerated by the presence of PPh3 and affords OPPh3. O-18 isotope tracing shows that H2O is the source of oxygen transferred to PPh3.
• Sellmann, Dieter; Seubert, Bernd; Kern, Wolfgang, Zeitschrift fur Naturforschung, B: Chemical Sciences, 1991, vol. 46, # 11, p. 1435 - 1448
  作者：Sellmann, Dieter、Seubert, Bernd、Kern, Wolfgang、Knoch, Falk、Moll, Mathias

  DOI：——

  日期：——