trans-(triphenylphosphane)2PtH(SnCl3) | 18117-31-2

• 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-(triphenylphosphane)2PtH(SnCl3)
• 英文别名: trans-[HPt(SnCl3)(PPh3)2]；trans-[PtH(SnCl3)(PPh3)2]；trans-{PtH(SnCl3)(PPh3)2}；trans-PtH(SnCl3)(P(C6H5)3)2；trans-[Pt(H)(SnCl3)(PPh3)2]；trans-[Pt(H)(PPh3)(SnCl3)]
• CAS: 18117-31-2；82509-99-7；16902-94-6
• 化学式: C₃₆H₃₁Cl₃P₂PtSn
• 分子量: 945.739
• InChiKey: ZDIRIEROLHEKJH-UHFFFAOYSA-K

计算性质

• 辛醇/水分配系数(LogP)：
  8.31
• 重原子数：
  43.0
• 可旋转键数：
  9.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.0
• 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：

  trans-(triphenylphosphane)2PtH(SnCl3) 在 triphenyl phosphine 、 CO 、 dppe 作用下， 以 乙醇 、 二氯甲烷 、 甲苯 为溶剂， 生成 cis-{PtCl(COC5H11)dppe}
  参考文献：
  名称：

  铂-锡体系在烯烃加氢甲酰化反应中的化学计量模型反应

  摘要：

  The three independent steps involved in the hydroformylation process, insertion of the olefin, insertion of carbon monoxide, and hydrogenolysis, have been investigated with use of platinum-tin catalysts and 1-pentene as olefin at low pressure and temperature in CH2Cl2. In the temperature range 198-308 K, the three reactions can be studied consecutively. All the intermediates observed were prepared and characterized separately. The complex trans-[PtH(SnCl3)(PPh3)2] was used as the initial compound for this sequence. The hydrido complex crystallized in the monoclinic space group C2/c, with a = 31.345 (5) angstrom, b = 12.716 (3) angstrom, c = 18.135 (3) angstrom, beta = 96.5 (2)-degrees, Z = 8, and R (R(w)) = 0.056 (0.060) for 3235 independent reflections having I > 2.56-sigma(I). The large Pt-Sn bond (2.601 (1) angstrom) distance correlates satisfactorily with the low 1J(Pt-Sn) value. The Pt-Sn bond is necessary for the insertion of 1-pentene in the hydrido-platinum complex and for the hydrogenolysis of the acyl compounds under these mild conditions. The insertion of 1-pentene was observed at 198 K, giving the cis-alkyl complex; CO insertion took place after isomerization to the trans-alkyl complex. The instability of Pt-Sn and Pt-C bonds in the trans-acyl complex favors easy decarbonylation or loss of SnCl2, so any other platinum complex without tin accepts SnCl2 from the acyl complex. The hydrogenolysis of trans-[Pt(SnCl3)(COC5H11)(PPh3)2] under 1.5 bar of H2-CO (1:1) did not yield n-hexanal quantitatively; only 12% of n-hexanal was formed. Thus, decarbonylation was the main process observed. From the reactions studied, it is possible to propose the following order of Pt-Sn bond stability: trans-[Pt(SnCl3)(COC5H11)(PPh3)2] < [Pt(SnCl3)(C5H11)(PPh3)2] < trans-[PtH-(SnCl3)(PPh3)2] < [PtH(SnCl3)(CO)(PPh3)2] < [Pt(mu-Cl)(SnCl3)(PPh3)]2 < [PtCl(SnCl3)(PPh3)]- < [PtCl2(SnCl3)2]2-. The insertion reactions studied with cis-[PtCl2(olefin)(PR3)] as an olefin carrier and the hydrido-platinum complexes trans-[PtHCl(PPh3)2], trans-[PtH(SnCl3)(PPh3)2], and [PtH(SnCl3)-(CO)(PPh3)2] as hydrogen carriers exclude the participation of intermolecular steps by reaction of two different platinum complexes under the experimental conditions described.

  DOI：

  10.1021/om00058a019
• 作为产物：
  描述：

  trans-{PtCl(CO{SnCl2}C5H11)(PPh3)2} 在 CHCl₃ 、 H₂ 作用下， 以 二氯甲烷 、 氯仿 为溶剂， 生成 trans-(triphenylphosphane)2PtH(SnCl3)
  参考文献：
  名称：

  铂-锡体系在烯烃加氢甲酰化反应中的化学计量模型反应

  摘要：

  The three independent steps involved in the hydroformylation process, insertion of the olefin, insertion of carbon monoxide, and hydrogenolysis, have been investigated with use of platinum-tin catalysts and 1-pentene as olefin at low pressure and temperature in CH2Cl2. In the temperature range 198-308 K, the three reactions can be studied consecutively. All the intermediates observed were prepared and characterized separately. The complex trans-[PtH(SnCl3)(PPh3)2] was used as the initial compound for this sequence. The hydrido complex crystallized in the monoclinic space group C2/c, with a = 31.345 (5) angstrom, b = 12.716 (3) angstrom, c = 18.135 (3) angstrom, beta = 96.5 (2)-degrees, Z = 8, and R (R(w)) = 0.056 (0.060) for 3235 independent reflections having I > 2.56-sigma(I). The large Pt-Sn bond (2.601 (1) angstrom) distance correlates satisfactorily with the low 1J(Pt-Sn) value. The Pt-Sn bond is necessary for the insertion of 1-pentene in the hydrido-platinum complex and for the hydrogenolysis of the acyl compounds under these mild conditions. The insertion of 1-pentene was observed at 198 K, giving the cis-alkyl complex; CO insertion took place after isomerization to the trans-alkyl complex. The instability of Pt-Sn and Pt-C bonds in the trans-acyl complex favors easy decarbonylation or loss of SnCl2, so any other platinum complex without tin accepts SnCl2 from the acyl complex. The hydrogenolysis of trans-[Pt(SnCl3)(COC5H11)(PPh3)2] under 1.5 bar of H2-CO (1:1) did not yield n-hexanal quantitatively; only 12% of n-hexanal was formed. Thus, decarbonylation was the main process observed. From the reactions studied, it is possible to propose the following order of Pt-Sn bond stability: trans-[Pt(SnCl3)(COC5H11)(PPh3)2] < [Pt(SnCl3)(C5H11)(PPh3)2] < trans-[PtH-(SnCl3)(PPh3)2] < [PtH(SnCl3)(CO)(PPh3)2] < [Pt(mu-Cl)(SnCl3)(PPh3)]2 < [PtCl(SnCl3)(PPh3)]- < [PtCl2(SnCl3)2]2-. The insertion reactions studied with cis-[PtCl2(olefin)(PR3)] as an olefin carrier and the hydrido-platinum complexes trans-[PtHCl(PPh3)2], trans-[PtH(SnCl3)(PPh3)2], and [PtH(SnCl3)-(CO)(PPh3)2] as hydrogen carriers exclude the participation of intermolecular steps by reaction of two different platinum complexes under the experimental conditions described.

  DOI：

  10.1021/om00058a019

文献信息

• Hydride Route for the Palladium‐Catalysed Cyclocarbonylation of Monoterpenes
  作者：Duc Hanh Nguyen、Gábor Laurenczy、Martine Urrutigoïty、Philippe Kalck

  DOI：10.1002/ejic.200500136

  日期：2005.10

  This paper focuses on the mechanism by which a monoterpene undergoes a cyclocarbonylation reaction catalysed by a palladium complex. Evidence is provided, based on intermediate species observed under pressure or with various ligands, that the catalytic cycle follows a hydride route starting from [Pd(H)(SnCl3)L-2], The [Pd(H)(SnCl3)L-2] complexes (L = PPh3 or PCy3) have been observed for the first time

  本文重点研究单萜在钯配合物催化下发生环羰基化反应的机理。根据在压力下或使用各种配体观察到的中间物质，提供了证据表明催化循环遵循从 [Pd(H)(SnCl3)L-2] 开始的氢化物路线，[Pd(H)(SnCl3)L- 2] 复合物（L = PPh3 或 PCy3）已通过多核 NMR 光谱首次观察到。阳离子氢化物络合物或钯 (0) 前体显示无反应性或反应性差。与模型铂配合物化学相关的研究已检测到一种酰基铂物种。大多数观察都是对异胡薄荷醇、二氢月桂烯醇或异柠檬烯环羰基化成相应的内酯或环戊酮进行的。二氢月桂烯的使用使我们能够观察到酰基铂复合物和相应的难以捉摸的酰基钯物种。也证明了 SnCl2 的共催化作用。
• Metals in organic syntheses
  作者：Alberto Scrivanti、Adriano Berton、Luigi Toniolo、Carlo Botteghi

  DOI：10.1016/0022-328x(86)80399-0

  日期：1986.10

  Among the several hydrides formed when trans-[PtHClL2] (L = PPh3) reacts with Sncl2, only trans-[PtH(SnCl3)L2] rapidly inserts ethylene, at −80°C, to yield cis-[PtEt(SnCl3)L2]. At −10°C, cis-[PtEt(SnCl3)L2] irreversibly rearranges to the trans-isomer, thus indicating that the cis-isomer is the kinetically controlled species, and that the trans-isomer is thermodynamically more stable.

  在反式-[PtHClL 2 ]（L = PPh 3）与Sncl 2反应时形成的几种氢化物中，只有反式-[PtH（SnCl 3）L 2 ]在-80°C时迅速插入乙烯，生成顺式-[ PtEt（SnCl 3）L 2 ]。在-10℃下，顺式-[PtEt（SnCl 3）L 2 ]不可逆地重排成反式-异构体，因此表明顺式-异构体是动力学控制的物质，并且反式-异构体在热力学上更稳定。
• Alkyl derivatives of platinum and rhodium as intermediates in homogeneous reactions of olefin hydrogenation and isomerisation
  作者：V.S. Petrosyan、A.B. Permin、V.I. Bogdashkina、D.P. Krut'ko

  DOI：10.1016/0022-328x(85)87347-2

  日期：1985.9

  Literature data and results obtained on the mechanisms of olefin hydrogenation and isomerisation using platinum and rhodium complexes, in particular, with PtSn and RhSn bonds were analysed. The role of alkyl derivatives of platinum and rhodium in these reactions is discussed.

  分析了使用铂和铑配合物，特别是具有PtSn和RhSn键的烯烃加氢和异构化机理的文献数据和结果。讨论了铂和铑的烷基衍生物在这些反应中的作用。
• Antonov, P. G.; Kukushkin, Yu. N.; Mitronina, L. N., Russian Journal of Inorganic Chemistry, 1979, vol. 24, p. 557 - 560
  作者：Antonov, P. G.、Kukushkin, Yu. N.、Mitronina, L. N.、Vasil'ev, L. N.、Sass, V. P.

  DOI：——

  日期：——
• 31P and1H NMR study of reaction between hydride complexes of platinum and divalent tin halides
  作者：V. I. Bogdashkina、A. B. Permin、V. S. Petrosyan、V. I. Pol'shakov、O. A. Reutov

  DOI：10.1007/bf00949943

  日期：1982.5