CpW(CO)₃(SnPh₃)

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: CpW(CO)₃(SnPh₃)
• 英文别名: (η5-C5H5)(CO)3WSnPh3
• 化学式: C₂₆H₂₀O₃SnW
• 分子量: 683.003
• InChiKey: DJLCYBGWBMTHEG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.11
• 重原子数：
  31
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  3
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  CpW(CO)₃(SnPh₃) 、 triethyloxonium fluoroborate 在 LiMe 作用下， 以 乙醚 为溶剂， 以69%的产率得到{W(SnPh3)(CO)2(η-C5H5)C(OEt)Me}
  参考文献：
  名称：

  Synthesis and reactions of the carbene complexes [M(SnPh₃)(CO)₂{C(OEt)Ph}L](M = Mo or W; L =η-C₅H₅,η-C₅Me₅or indenyl), [M(SnPh₃)(CO)₂{C(OEt)Me}(η-C₅H₅)](M = Mo or W) and [MI(CO)₂{C(OEt)R}(η-C₅H₅)](M = Mo or W, R = Me or Ph). X-Ray crystal structures of [Mo(SnPh₃)(CO)₂{C(OEt)Ph}(η-C₅Me₅)] and [WI(CO)₂{C(OEt)Ph}(η-C₅H₅)]

  摘要：

  Treatment of the tricarbonyls [M(SnPh3)(CO)3L] [M = Mo or W; L = eta-C5H5, eta-C5Me5 or eta-5-C9H7-(indenyl)] with LiPh followed by [OEt3][BF4] results in the formation of the carbenes [M(SnPh3)-(CO)2{ = C(OEt)Ph}L] in good to high yields. Related reactions of [M(SnPh3)(CO)3(eta-C5H5)] but using LiMe afford [M(SnPh3)(CO)2{= C(OEt)Me}(eta-C5H5)]. The complex trans-[M(SnPh3)(CO)2{= C-(OEt)Ph}(eta-C5Me5)] is monoclinic, a = 14.611(36), b = 16.788(20), c = 16.183(30) angstrom, beta = 96.08(18)-degrees, and R = 0.0888 for 2117 independent reflections. While the eta-C5H5 and indenyl complexes exist as pairs of isomers in solution generated by rotation about the M = C(carbene) bond, the eta-C5Me5 complexes exist as single isomers in solution. Treatment of [M(SnPh3)(CO)2{= C(OEt)Ph}(eta-C5H5)] (M = Mo or W) with I2 results in formation of the iodometal species [MI(CO)2{= C(OEt)Ph}(eta-C5H5)]. The complex [WI(CO)2{= C(OEt)Ph}(eta-C5H5)] is monoclinic, a = 9.34(3), b = 13.00(2), c = 13.53(3) angstrom, beta = 97.8(2)-degrees, and R = 0.0812 for 2091 independent reflections. In solution this compound exists as three trans isomers and one cis. Treatment of [M(SnPh3)(CO)2{= C(OEt)Ph}(eta-C5Me5)] with I2 results in the eventual formation of [MoPh(CO)3(eta-C5Me5)] in the molybdenum case and [MI3-(CO)2(eta-C5Me5)] in both cases.

  DOI：

  10.1039/dt9910000749
• 作为产物：
  描述：

  bis(tricarbonyl(η-cyclopentadienyl)tungsten) 、 三苯基氢化锡 以 5,5-dimethyl-1,3-cyclohexadiene 为溶剂， 反应 1.0h， 以38%的产率得到CpW(CO)₃(SnPh₃)
  参考文献：
  名称：

  Reactions of [CpM(CO)₃]₂ (M = Mo, W) with Ph₃SnSR: formation of CpM(CO)₃(SnPh₃) and CpM(CO)₂(κ²-SR) via Sn–S bond cleavage

  摘要：

  The mixed-metal compounds CpM(CO)(3)(SnPh3) (1, M=Mo; 2, M=W) are obtained as the only isolable products from the reactions of [CpM(CO)(3)](2) with PhSSnPh3, whereas similar reactions with pymSSnPh(3) (pymS=pyrimidine-2-thiolate) lead to the formation of chelate compounds CpM(CO)(2)((2)-pymS) (3, M=Mo; 4, M=W). Separate experiments show that CpM(CO)(3)(SnPh3) are precursors of CpM(CO)(2)((2)-pymS). CpM(CO)(3)(SnPh3) can also be synthesized in slightly improved yield from the direct reaction between [CpM(CO)(3)](2) and Ph3SnH, while the yield of CpM(CO)(2)((2)-pymS) becomes negligible when [CpM(CO)(3)](2) is treated with pymSH.

  DOI：

  10.1080/00958972.2015.1033411

文献信息

• New routes to molybdenum and tungsten carbyne complexes [M(CO)₂(CPh)(η-C₅H₄R)](M = Mo or W, R = SnPh₃; M = W, R = H)
  作者：Harry Adams、Neil A. Bailey、Gary W. Bentley、Jayne E. Muir、Mark J. Winter

  DOI：10.1039/c39950000515

  日期：——

  Treatment of the ethoxy carbenes [M(SnPh3)(CO)2C(OEt)Ph}(η-C5H5)](M = Mo or W) with LDA or LDA/HMPA followed by PhC(O)Cl results in the carbyne complexes [M(CO)2(CPh)(η-C5H4SnPh3)]via anions [M(CO)2C(OEt)Ph}(η-C5H4SnPh3)]–, while treatment of [W(SnPh3)(CO)3(η-C5H5)] with LiPh followed by TMEDA/MeC(O)Cl results in the carbyne [W(CO)2(CPh)(η-C5H5)].

  用 LDA 或 LDA/HMPA 处理乙氧基卡宾 [M(SnPh3)(CO)2C(OEt)Ph}(δ-C5H5)](M = Mo 或 W)，然后用 PhC(O)Cl 处理，结果为碳炔配合物 [M(CO)2(CPh)(δ-C5H4SnPh3)] 通过阴离子 [M(CO)2C(OEt)Ph}(δ-C5H4SnPh3)]–，同时处理 [W (SnPh3)(CO)3(δ- )] 与 LiPh 反应，然后 TMEDA/MeC(O)Cl 产生碳炔 [W(CO)2(CPh)(δ- )]。
• Cervantes, Jorge; Vincenti, Steven P.; Kapoor, Ramesh N., Organometallics, 1989, vol. 8, # 3, p. 744 - 748
  作者：Cervantes, Jorge、Vincenti, Steven P.、Kapoor, Ramesh N.、Pannell, Keith H.

  DOI：——

  日期：——
• Study of the reactions of halogen and mercury halogen derivatives of metal carbonyls with samarium and ytterbium
  作者：G. Z. Suleimanov、V. N. Khandozhko、R. Yu. Mekhdiev、P. V. Petrovskii、I. M. Yanovskaya、O. L. Lependina、N. E. Kolobova、I. P. Beletskaya

  DOI：10.1007/bf00965385

  日期：1988.3
• Synthesis and reactions of LM(SnPh3)(CO)2{C(OEt)Ph} (L = C5Me5 or η5-C9H7; M = Mo or W)
  作者：Gary W. Bentley、Gordon Hough、Mark J. Winter、Simon Woodward

  DOI：10.1016/s0277-5387(00)80674-9

  日期：1989.1