| 113380-14-6

• CAS: 113380-14-6
• 化学式: C₂₃H₅₃O₂P₄SiTa
• 分子量: 694.601
• InChiKey: MPCKOSFSPKYENZ-UHFFFAOYSA-N

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：

  在 (i-Pr)3SiOTf 作用下， 以 further solvent(s) 为溶剂， 生成 Ta(i-Pr)3SiOCCOSi(i-Pr)3(dmpe)2OTf
  参考文献：
  名称：

  由羰基金属和异氰化物配合物生成的卡宾；羰基和 CNR 配体还原偶联的中间体

  摘要：

  Isolement et caracterisation structuree d'un intermediaire-cle dans le couplage reductif de CO, [M(CO){COSi(i-Pr) 3 }(dmpe) 2 ] (M=Nb, Ta)。[Re(CNHR)(CNR) 2 (PMePh 2 ) 2 Cl] +

  DOI：

  10.1021/ja00216a062
• 作为产物：
  描述：

  {Ta(CO)2(dmpe)2Cl} 在 Na/Hg 、 (i-Pr)3SiCl 作用下， 以 四氢呋喃 为溶剂， 以90%的产率得到
  参考文献：
  名称：

  由羰基金属和异氰化物配合物生成的卡宾；羰基和 CNR 配体还原偶联的中间体

  摘要：

  Isolement et caracterisation structuree d'un intermediaire-cle dans le couplage reductif de CO, [M(CO){COSi(i-Pr) 3 }(dmpe) 2 ] (M=Nb, Ta)。[Re(CNHR)(CNR) 2 (PMePh 2 ) 2 Cl] +

  DOI：

  10.1021/ja00216a062

文献信息

• Mechanistic studies of the reductive coupling of carbon monoxide in seven-coordinate niobium(I) and tantalum(I) dicarbonyl complexes
  作者：Raymond N. Vrtis、Shuncheng Liu、C. Pulla Rao、Simon G. Bott、Stephen J. Lippard

  DOI：10.1021/om00047a061

  日期：1991.1

  The mechanism by which the two carbonyl ligands in the seven-coordinate complexes [M(CO)2(dmpe)2Cl] [M = Ta, Nb; dmpe = 1,2-bis(dimethylphosphino)ethane] are reductively coupled has been elucidated. The first step involves two-electron reduction to afford the [M(CO)2(dmpe)2]- anion, the tantalum analogue of which was structurally characterized as the tetra-hexylammonium salt. The geometry of this anion is distorted octahedral with cis-carbonyl ligands. Reaction of the anion with 1 equiv of trialkylsilyl chloride yields the siloxycarbyne species [M(= COSiR3)(CO)(dmpe)2] (M = Ta or Nb), formed by electrophilic attack of the silyl halide on the carbonyl oxygen atom. The tantalum triisopropylsiloxycarbyne complex, the X-ray structural analysis of which is described, reacts with 1 equiv of trimethylsilyl chloride to afford the asymmetric acetylene complex, [TaMe3SiOC = COSi(iota-Pr)3}(dmpe)2Cl], which was also structurally characterized. The transition state between the carbyne and coupled products may be an eta2-ketenyl of the type [Taeta2-(O)CCOSiR3}(dmpe)2X]- (X = halide). Such an assignment is supported by a series of experiments involving addition of different silyl halide reagents (Me3SiX; X = Cl, I, OTf) to (n-C6H13)4N[Ta(CO)2(dmpe)2]. The generality of the reaction mechanism is discussed.
• 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
• Vrtis, Raymond N.; Bott, Simon G.; Lippard, Stephen J., Organometallics, <hi>1992</hi>, vol. 11, # 1, p. 270 - 277
  作者：Vrtis, Raymond N.、Bott, Simon G.、Lippard, Stephen J.

  DOI：——

  日期：——