{PtH(SnCl3)(CO)(PPh3)2} | 72794-37-7

• 英文名称: {PtH(SnCl3)(CO)(PPh3)2}
• CAS: 72794-37-7
• 化学式: C₃₇H₃₁Cl₃OP₂PtSn
• 分子量: 973.749
• InChiKey: IQJZMVNHRRCCIH-UHFFFAOYSA-K

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：

  {PtH(SnCl3)(CO)(PPh3)2} 在 triphenyl phosphine 作用下， 以 二氯甲烷 为溶剂， 生成 {PtH(PPh3)3}(1+)
  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(COC5H11)(PPh3)2} 在 CHCl₃ 、 H₂ 、 CO 作用下， 以 二氯甲烷 、 氯仿 为溶剂， 生成 {PtH(SnCl3)(CO)(PPh3)2}
  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

• 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。