cis-{Pt(PEt3)2(n-propyl)2} | 17764-65-7

• 分子结构分类: 有机化合物 - 有机磷化合物 - 有机膦及其衍生物
• 英文名称: cis-{Pt(PEt3)2(n-propyl)2}
• 英文别名: cis-[Pt(n-Pr)2(PEt3)2]；cis-[Pt(n-propyl)2(PEt3)2]
• CAS: 17764-65-7
• 化学式: C₁₈H₄₄P₂Pt
• 分子量: 517.575
• InChiKey: PVWFZRUJTXZFLG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.78
• 重原子数：
  21.0
• 可旋转键数：
  12.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  cis-{Pt(PEt3)2(n-propyl)2} 在 盐酸 作用下， 以 乙醚 为溶剂， 生成 trans-{Pt(PEt3)2(n-propyl)Cl}
  参考文献：
  名称：

  Alibrandi, Giuseppe; Cusumano, Matteo; Minniti, Domenico, Inorganic Chemistry, 1989, vol. 28, # 2, p. 342 - 347

  摘要：

  DOI：

文献信息

• β-Hydrogen Kinetic Effect
  作者：Raffaello Romeo、Giuseppina D'Amico、Emilia Sicilia、Nino Russo、Silvia Rizzato

  DOI：10.1021/ja0702162

  日期：2007.5.1

  A combined kinetic and DFT study of the uncatalyzed isomerization of cationic solvent complexes of the type cis-[Pt(R')(S)(PR3)(2)](+) (R' = linear and branched alkyls or aryls and S = solvents) to their trans isomers has shown that the reaction goes through the rate-determining dissociative loss of the weakly bonded molecule of the solvent and the interconversion of two geometrically distinct T-shaped 14-electron three-coordinate intermediates. The Pt-S dissociation energy is strongly dependent on the coordinating properties of S and independent of the nature of R'. The energy barrier for the fluxional motion of [Pt(R')(PR3)(2)](+) is comparatively much lower (approximate to 8-21 kJ mol(-1)). The presence of beta-hydrogens on the alkyl chain (R' = Et, Pr-n, and Bu-n) produces a great acceleration of the reaction rate. This accelerating effect has been defined as the beta-hydrogen kinetic effect, and it is a consequence of the stabilization of the transition state and of the cis-like three-coordinate [Pt(R')(PR3)(2)](+) intermediate through an incipient agostic interaction. The DFT optimization of [Pt(R')(PMe3)(2)](+) (R' = Et, Pr-n, and Bu-n) reproduces a classical dihapto Pt center dot center dot center dot center dot eta(2)-HC agostic mode between the unsaturated metal and a dangling C-H bond. The value of the agostic stabilization energy (in the range of approximate to 21-33 kJ mol(-1)) was estimated by both kinetic and computational data and resulted in being independent of the length of the hydrocarbon chain of the organic moiety. A better understanding of such interactions in elusive reaction intermediates is of primary importance in the control of reaction pathways, especially for alkane activation by metal complexes.
• Romeo, Raffaello; Plutino, Maria Rosaria; Elding, Lars I., Inorganic Chemistry, 1997, vol. 36, # 25, p. 5909 - 5916
  作者：Romeo, Raffaello、Plutino, Maria Rosaria、Elding, Lars I.

  DOI：——

  日期：——