{Ta(Me3SiOCCOSiMe3)(dmpe)2Cl} | 99797-93-0

• 英文名称: {Ta(Me3SiOCCOSiMe3)(dmpe)2Cl}
• 英文别名: cis-{Ta(Me3SiOCCOSiMe3)(dmpe)2Cl}
• CAS: 99797-93-0
• 化学式: C₂₀H₅₀ClO₂P₄Si₂Ta
• 分子量: 719.083
• InChiKey: GKWXDBQHOKBQES-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  {Ta(Me3SiOCCOSiMe3)(dmpe)2Cl} 在 HCl aq. 作用下， 以 四氢呋喃 为溶剂， 以94%的产率得到{tantalum(H)(HOCCOH)(bis(1,2-dimethylphosphino)2ethane)2Cl}Cl
  参考文献：
  名称：

  Vrtis, Raymond N.; Bott, Simon G.; Lynn Rardin, Organometallics, 1991, vol. 10, # 5, p. 1364 - 1373

  摘要：

  DOI：
• 作为产物：
  描述：

  三甲基氯硅烷 、 以 四氢呋喃 为溶剂， 生成 {Ta(Me3SiOCCOSiMe3)(dmpe)2Cl}
  参考文献：
  名称：

  Vrtis, Raymond N.; Bott, Simon G.; Lippard, Stephen J., Organometallics, 1992, vol. 11, # 1, p. 270 - 277

  摘要：

  DOI：

文献信息

• Reductive coupling of two carbon monoxide ligands to form a coordinated alkyne
  作者：Patricia A. Bianconi、Ian D. Williams、Mary P. Engeler、Stephen J. Lippard

  DOI：10.1021/ja00262a030

  日期：1986.1

  Etude du couplage reducteur de CO pour former une nouvelle espece de produit derive de CO, Me 3 SiOC≡COSiMe 3 stabilise par coordination a Ta. Structure moleculaire du produit obtenu: [Ta(Me 3 SiOC≡COSiMe 3 )(dmpe) 2 Cl]

  Etude du couplage reducteur de CO 浇注前 une nouvelle espece de produit Derive de CO, Me 3 SiOC≡COSiMe 3 稳定标准配位 a Ta。结构分子 obtenu: [Ta(Me 3 SiOC≡COSiMe 3 )(dmpe) 2 Cl]
• Protasiewicz, John D.; Lippard, Stephen J., Journal of the American Chemical Society, 1991, vol. 113, # 18, p. 6564 - 6570
  作者：Protasiewicz, John D.、Lippard, Stephen J.

  DOI：——

  日期：——
• Bianconi, Patricia A.; Vrtis, Raymond N.; Rao, Ch. Pulla, Organometallics, 1987, vol. 6, # 9, p. 1968 - 1977
  作者：Bianconi, Patricia A.、Vrtis, Raymond N.、Rao, Ch. Pulla、Williams, Ian D.、Engeler, Mary P.、Lippard, Stephen J.

  DOI：——

  日期：——
• Electrophile-Promoted Carbyne-CO Coupling at a Tantalum Center
  作者：John D. Protasiewicz、Brian S. Bronk、Axel Masschelein、Stephen J. Lippard

  DOI：10.1021/om00016a037

  日期：1994.4

  Siloxycarbyne complexes of the type [Ta(=COSiR3) (CO) (dmpe)2], R3 = (t)BuPh2 (1b) or Ph3 (1c), have been prepared by routes analogous to those previously described for [Ta(=COSi-(i)Pr3)(CO)(dmpe)2] (1a). Compounds 1a-c react with R'3SiCl to afford the acetylene complexes [Ta(R3SiOC=COSiR'3)(dmpe)2Cl] (R3 = (i)Pr3, R'3 = Me3 (2a); R3 = (t)BuPh2, R'3 = Me3 (2b); R3 = Ph3, R'3 = Me3 (2c); R3 = (t)BuPh2, R'3 = Et3 (2d)). The mechanism of C-C bond formation in these systems has been elucidated by stopped-flow kinetic studies of the reaction of 1a with excess Me3SiCl in THF to form 2a. Addition of (n-pentyl)4NCl increased the rate of reaction between 1a and excess Me3SiCl, but produced [Ta(Me3SiOC=COSiMe3)(dmpe)2Cl] rather than 2a. A pathway for chloride-induced exchange of silyl groups between the starting material and excess Me3SiCl has been elucidated. Addition of (n-butyl)4NBPh4 also strongly accelerated the observed reaction rates, but in this case the product formed was 2a. The observed rate increases were attributed to an increase in the ionic strength of the solution. At a constant salt concentration of 23.9 mM (n-butyl)4NBPh4, the reaction was first order in both 1a and Me3SiCl, with a second order rate constant of 1.71 +/- 0.04 M-1 s-1 at 22 +/- 1-degrees-C. These results are consistent with a mechanism involving electrophilic attack by the silyl reagent on the CO ligand of 1 as the rate-determining step of the reaction. Addition of AlEt3 to lb allowed the isolation of [Ta(=COSi(t)BuPh2)(COAlEt3)(dmpe)2] (3b), a model for the initial species formed upon silylation of the CO ligand in 1b. Comparison of the spectroscopic and structural properties of 3b with those of 1b revealed that C-C bond formation does not occur upon addition of this particular Lewis acid. The structure of 3b revealed several important features, the most significant of which is a decrease in the C-Ta-C angle to 73.4(4)degrees from the value of 89.1(3)degrees in 1b. The corresponding angle in the reductively coupled product, [Ta(Et3SiOC=COSi(t)BuPh2)(dmpe)2Cl] (2d), the structure of which is also reported, is 36.5(2)degrees.
• Kinetic, spectroscopic, and structural evidence for carbene-carbyne intermediates in carbyne/CO coupling
  作者：John D. Protasiewicz、Axel Masschelein、Stephen J. Lippard

  DOI：10.1021/ja00055a074

  日期：1993.1