trans-[PtPh2(PMe2Ph)2] | 27072-43-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: trans-[PtPh2(PMe2Ph)2]
• 英文别名: benzene;dimethyl(phenyl)phosphane;platinum(2+)
• CAS: 27072-43-1
• 化学式: C₂₈H₃₂P₂Pt
• 分子量: 625.59
• InChiKey: VGOFREPNBVSCLQ-UHFFFAOYSA-N

计算性质

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

反应信息

• 作为反应物：
  描述：

  ((CH₃)2(C₆H₅)P)2PtI₂ 、 trans-[PtPh2(PMe2Ph)2] 以 二氯甲烷 为溶剂， 生成 trans-[PtIPh(PMe2Ph)2]
  参考文献：
  名称：

  铂（II）配合物中的烷基交换反应及其催化

  摘要：

  OT的symmetrisation反应[PTR的研究2大号2 ]与[PTX 2大号2 ]得到[PtXRL 2 ]的情况下（R = Me中，pH值，或C CME; L = PET 3，PME 3，PME 2 Ph或AsMe 3； X = Cl，I，NCS，NO 2或NO 3）。研究了反应速率和立体化学对取代基R，X和L的依赖性，并讨论了反应机理。的反应顺式- [氯铂酸2（PME 2 PH）2 ]与顺式- [PTME 2（PME2 Ph） 2 ]产生顺式-[PtClMe（PMe 2 Ph） 2 ]被[Pt 2 Cl 4（PMe 2 Ph） 2 ]催化，但在与顺式-[PtMe 2（ PMe 2 Ph） 2 ]得到顺式-[Pt 2（μ-Cl） 2 Me 2（PMe 2 Ph） 2 ]。

  DOI：

  10.1039/dt9770001219
• 作为产物：
  描述：

  trans-PtPh(Ph3Ge)(PMe2Ph)2 以 氘代苯 为溶剂， 生成 trans-[PtPh2(PMe2Ph)2] 、 tetrakis(dimethylphenylphosphine)platinum(0) 、 四苯基锗
  参考文献：
  名称：

  顺式和反式双（三苯基锗基）双（叔膦）铂（II）的热反应性

  摘要：

  复杂的顺式-Pt（Ph 3 Ge）2（PMe 2 Ph）2进行平滑异构化，在室温下通过缔合的五配位中间体生成反式异构体。获得了顺式至反式异构化的热力学参数和活化能，分别为ΔH ＃  = 105 kJ mol -1，ΔS ＃  = 12.5 J mol -1  K -1和Ea  = 107 kJ mol -1。反式-Pt（Ph 3 Ge）的加热2（PMe 2 Ph）2在50°C下放置36天会生成反式-PtPh（Ph 3 Ge）（PMe 2 Ph）2，然后形成反式-PtPh 2（PMe 2 Ph）2，Pt（PMe 2 Ph） ）4，而Ph 4葛最终经由从pH值苯基基团的消去3葛配体随pH的解放2葛单元和其余的博士的后续还原消除3在80℃下1个月的Ge配体。

  DOI：

  10.1016/j.jorganchem.2006.05.065

文献信息

• Reaction Mechanism of Transmetalation between Tetraorganostannanes and Platinum(II) Aryltriflate Complexes. Mechanistic Model for Stille Couplings
  作者：Patrik Nilsson、Graeme Puxty、Ola F. Wendt

  DOI：10.1021/om051021a

  日期：2006.2.1

  The complexes trans-[PtPh(OTf)(PMe2Ph)(2)] (1) and trans- [PtPh(OTf)(PPh3)(2)] (4) were synthesized from the corresponding chloro complexes in moderate yields. Complex I is slowly hydrolyzed in solution, giving the dinuclear hydroxo-bridged complex [Pt(mu-OH)(PMe2Ph)(2)](2)(CF3SO3)(2) (6), which was characterized by X-ray crystallography. In solution I and 4 undergo fast solvolysis to give the corresponding solvento cations. The reactivities of 1 and 4 with Me3SnPh were investigated in different solvents, and with 1 two products, trans- [PtPh2(PMe2Ph)(2)] (8) and cis-[PtPh2(PMe2Ph)(2)] (9), were always formed simultaneously. In THF an intermediate, trans- [PtPhMe(PMe2Ph)(2)] (14), was characterized on the path to 9. The kinetics for these reactions were evaluated numerically, and on the basis of rate laws, activation parameters, and reactivity trends a mechanism involving parallel equilibria to 8 and 9 with associative activation in all steps is proposed. In this mechanism the initial attack always takes place trans to the phenyl group, giving 8 and 14, respectively, via an open transition state. In a subsequent reaction, 14 reacts with another molecule of stannane, giving 9 as the final product via a cyclic transition state. Complex 4 gives exclusive formation of cis products: cis-[PtPhMe(PPh3)2] (12) and cis-[PtPh2(PPh3)2] (13). These results are discussed in relation to the reaction mechanism of the transmetalation step in the Stille reaction.