cis-{Pt(PEt3)2(Et-d5)2} | 117605-17-1

• 分子结构分类: 有机化合物 - 有机磷化合物
• 英文名称: cis-{Pt(PEt3)2(Et-d5)2}
• 英文别名: cis-[Pt(ethyl-d5)2(PEt3)2]
• CAS: 117605-17-1
• 化学式: C₁₆H₄₀P₂Pt
• 分子量: 499.442
• InChiKey: WZUMXZDTZGZYQZ-ZWCUISAJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.0
• 重原子数：
  19.0
• 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(Et-d5)2} 在 CF₃SO₃H 作用下， 以 氘代乙腈 为溶剂， 生成 cis-[Pt(ethyl-d5)(CD3CN)(PEt3)2](1+)
  参考文献：
  名称：

  β-Hydrogen Kinetic Effect

  摘要：

  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.

  DOI：

  10.1021/ja0702162

文献信息

• Apparent fluxionality in diethyl(triethylphosphine)platinum(II), a coordinatively unsaturated intermediate in .beta.-hydride elimination
  作者：Thomas J. McCarthy、Ralph G. Nuzzo、George M. Whitesides

  DOI：10.1021/ja00397a014

  日期：1981.4

  deuterated complex 5 was synthesized by using conventional techniques and decomposcd in cyclohexane solution at 118 oC for t h (Schemc II). Under these conditions, dissociation of L is rate limiting, and no isotope effect (kslko = 1.0 + 0.1) is observed on comparison of thc rates of decomposition of LrPt-Abstract: The thermal decomposition of (Et3P)2Pt(C2H5)2 proceeds by rate-limiting dissociation of triethylphosphine

  环己烷溶液中二乙基双（三乙基膦）铂（II）（l）的热分解机理在 Schemc la 中进行了总结，在没有添加 L 的情况下，L (l * 2) 的初始损失是限速的。配位不饱和的 14-电子物种 2 似乎具有高反应性：转化 2-3 比 |-2 或 3 _ 4.4 具有组成 LMR2 的物种是其他对氢化物消除的重要中间体，包括铂 6 和镍 T 和在未活化的 ^y、6 和 e CH 键氧化添加到铂 (ll) 的反应中。E'e 虽然没有关于 2 的几何结构的实验信息，但相关物种 (Ph3P)rRh-(I)+ClO4 - 是“T”形，r0 和 cis-(CH3)2Au(H2O)Tf 是方形平面。l' 本文提供的证据表明，三配位物质 2 中与铂键合的两个乙基在对氢消除方面是等效的。这种等价性可能反映了三乙基膦 (2a + 2b) 或乙基 (2a-2c) 的运动，这些运动相对于 3 到 4 的后续转化、2
• Alibrandi, Giuseppe; Cusumano, Matteo; Minniti, Domenico, Inorganic Chemistry, 1989, vol. 28, # 2, p. 342 - 347
  作者：Alibrandi, Giuseppe、Cusumano, Matteo、Minniti, Domenico、Scolaro, Luigi Monsù、Romeo, Raffaello

  DOI：——

  日期：——