(η(5)-C5H5)W(CO)2(PPh3)(COMe) | 53079-50-8

• 英文名称: (η(5)-C5H5)W(CO)2(PPh3)(COMe)
• CAS: 53079-50-8
• 化学式: C₂₇H₂₃O₃PW
• 分子量: 610.302
• InChiKey: ZSZKDWWXZZSPPF-UHFFFAOYSA-N

反应信息

• 作为反应物：
  描述：

  (η(5)-C5H5)W(CO)2(PPh3)(COMe) 以 四氢呋喃 为溶剂， 生成 tricarbonyl(cyclopentadienyl)methyltungsten(II)
  参考文献：
  名称：

  Tyler, David R., Inorganic Chemistry, 1981, vol. 20, # 7, p. 2257 - 2261

  摘要：

  DOI：
• 作为产物：
  描述：

  (η5-C5H5)W(CO)3CH2SiMe3 在 PPh₃ 作用下， 以 正己烷 为溶剂， 生成 (η(5)-C5H5)W(CO)2(PPh3)(COMe)
  参考文献：
  名称：

  Chen, Jhy-Der; Wu, Chun-Kuei; Wu, Iuan-Yuan, Journal of Organometallic Chemistry, 1993, vol. 454, p. 173 - 182

  摘要：

  DOI：

文献信息

• Formation of the alkoxyalkyl complexes [M{CHMe(OMe)}(CO)₂(η-C₅H₄R)](M = Mo, R = H; M = W, R = H or Me) and their transformations by loss of MeOH into η³-propenoyl or vinyl complexes. Crystal structures of [Mo{CHMe(PPh₃)}(CO)₂(PPh₃)(η-C₅H₅)]BF₄, [Mo(η³-CH₂CHCO)(CO)(PPh₃)(η-C₅H₅)] and [W(σ-CHCH₂)(CO)₂(PPh₃)(η-C₅H₄Me)]
  作者：Harry Adams、Neil A. Bailey、J. Trevor Gauntlett、Ian M. Harkin、Mark J. Winter、Simon Woodward

  DOI：10.1039/dt9910001117

  日期：——

  Addition of MeSO3F or [Me3O]BF4 followed by PPh3 to the aldehyde complex [Mo(MeCHO)(CO)2(eta-C5H5)]- results in formation of the methoxyalkyl complex trans-[MoCHMe(OMe)}(CO)2(PPh3)(eta-C5H5)] in a reaction that proceeds via the unstable [Moeta-2-CHMe(OMe)}(CO)2(eta-C5H5)]. A by-product of this reaction is the ylide trans-[MoCHMe(PPh3)}(CO)2(PPh3)(eta-C5H5)]X (X = BF4- or SO3F-), a species (X = BF4) better prepared by treatment of trans-[MoCHMe(OMe)}(CO)2(PPh3)(eta-C5H5)] with HBF4 in the presence of PPh3. The crystalline ylide trans-[MoCHMe(PPh3)}(CO)2(PPh3)(eta-C5H5)]BF4 is monoclinic, with a = 11.378(34), b = 18.903(35), c = 20.17(8) angstrom, beta = 115.28(31)-degrees and for the 3918 independent reflections with I/sigma(I) > 3.0, R = 0.0510. In solution, trans-[MoCHMe(OMe)}(CO)2(PPh3)(eta-C5H5)] either degrades to [MoH(CO)2(PPh3)(eta-C5H5)] or loses MeOH to form the eta-3-propenoyl [Mo(eta-3-CH2CHC = O)(CO)(PPh3)(eta-C5H5)]. This molecule is monoclinic, with a = 17.231(50), b = 8.189(14), c = 16.727(36) angstrom, beta = 106.79(22)-degrees and for the 1654 independent reflections for which \F\/sigma(\F\) > 4.0, R = 0.100. The proposed mechanism for its formation is based on isotopic tracking experiments and includes a vinyl to carbonyl migration. Treatment of [WMe(CO)3(eta-C5H4R)] (R = H or Me) with PPh3 in MeCN gives the acyl [W(sigma-COMe)(CO)2(PPh3)(eta-C5H4R)]. These react with [Me3O][BF4] to form the cationic carbenes [W = CMe(OMe)}(CO)2(PPh3)(eta-C5H4R)]BF4, which in turn react with LiBHEt3 to give the alkoxyalkyls trans-[WCHMe(OMe)}(CO)2(PPh3)(eta-C5H4R)]. The alkoxyalkyls trans-[WCHMe(OMe)}(CO)2(PPh3)(eta-C5H4R)] react with traces of acid to form the sigma-vinyls trans-[W(sigma-CH = CH2)(CO)2(PPh3)(eta-C5H4R)], the methylcyclopentadienyl species of which is crystalline, monoclinic, with a = 36.952(40), b = 10.971(13), c = 25.148(23) angstrom and beta = 103.60(8)-degrees. For the 2542 independent reflections for which \F\/sigma(\F\) > 5.0, R converged to 0.0750.
• Solvent-Free Organometallic Migratory Insertion Reactions
  作者：Olalere G. Adeyemi、Neil J. Coville

  DOI：10.1021/om0301738

  日期：2003.5.1

  Migratory insertion reactions of organometallic complexes have been shown to occur in the absence of solvent and, more significantly, between solid reagents. Reaction between eta(5)-C5H5)M(CO)(3)Me (M = Mo, W) or (,eta(5)-C5H5)Fe(CO)(2)Me and PPh3 (no solvent) took place at temperatures between 40 and 90 degreesC and gave the products (eta(5)-C5H5)M(CO)(2)(PPh3)COMe and (eta(5)-C5H5)Fe(CO)(PPh3)COMe in moderate to good yield (60-99%). The Mo and W complexes reacted in the solid state when T < 80 degreesC. The decarbonylation of (eta(5)-C5H5)MO(CO)(2)(PPh3)COMe to yield (eta(5)-C5H5)Mo(CO)(2)(PPh3)Me also occurred in the solid state (120 degreesC). Reaction of (eta(5)-C5H5)MO(CO)(3)Me with a range of ligands, L (L = PPh3, P(p-MeOC6H4)(3), PCy3, PEt3, AsPh3, POPh3, P(OEt)(3); 1:1 reagent ratio, 90 degreesC, 15 min), in the absence of solvent gave (eta(5)-C5H5)Mo(CO)(2)(L)COMe (7-100% yield) and, on extended reaction, (eta(5)-C5H5)Mo(CO)(2)(L)Me in varying yields. A kinetic study of the solid-state reaction between (eta(5)-C5H5)Mo(CO)(3)Me and PPh3 yielded rate constants, e.g. k = 5.18 x 10(-5)s(-1) (Mo:p = 1:10; 50 degreesC), which compares with the literature solution data in toluene (k = (0.8-2.5) X 10(-5) s(-1), 50 degreesC) using similar metal to ligand ratios. The data are consistent with a pseudo-first-order reaction in the presence of PPh3. Diffusional effects on the reaction rate are detected at low temperature and low PPh3 ratios.