(3-methylbut-2-enoyl)bis(triphenyl-l5-phosphaneyl)platinum(IV) chloride | 138813-40-8

• 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: (3-methylbut-2-enoyl)bis(triphenyl-l5-phosphaneyl)platinum(IV) chloride
• CAS: 138813-40-8
• 化学式: C₄₁H₃₇ClOP₂Pt
• 分子量: 838.225
• InChiKey: ILCAKHHXUZOICH-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  8.61
• 重原子数：
  46.0
• 可旋转键数：
  10.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.05
• 拓扑面积：
  17.07
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  (3-methylbut-2-enoyl)bis(triphenyl-l5-phosphaneyl)platinum(IV) chloride 、 silver trifluoromethanesulfonate 以 乙腈 为溶剂， 以89%的产率得到
  参考文献：
  名称：

  金属介导的乙烯基亲电子体的羰基烷氧基化反应的机理。1.乙烯基酰基铂（II）配合物的制备，分子结构和醇解

  摘要：

  The two key steps of the nickel triad metal-mediated carbalkoxylation of vinyl electrophiles were investigated using platinum complexes: (a) carbonyl insertion of sigma-vinyl Pt(II) halides and (b) alcoholysis of vinylic acyl Pt(II) complexes. NMR spectral studies suggest that the carbonyl insertion into the alkenyl C-Pt bond proceeds via the formation of a sigma-vinyl Pt(II) carbonyl species, followed by phosphine dissociation and migratory insertion. While the resulting vinylic acyl Pt(II) halides are unreactive toward alcohols, the corresponding cationic triflate complexes readily undergo alcoholysis in the absence of base. Kinetic and NMR spectral studies establish that the alcoholysis of vinylic acyl Pt(II) triflate complexes occurs via a preequilibration to form a reactive, trigonal-planar intermediate, followed by the rate-determining trans-cis isomerization and nucleophilic attack of alcohols prior to the facile reductive elimination to the alpha,beta-unsaturated carboxylic esters. Both the covalent and cationic vinylic acyl Pt(II) complexes were isolated and fully characterized. A single-crystal molecular structure determination is reported for trans-(CH3)2C = CCOPt(PPh3)2I (9b). Complex 9b crystallizes in the monoclinic space group P2(1)/n with a = 11.924 (5) angstrom, b = 20.354 (10) angstrom, c = 15.606 (7) angstrom, beta = 105.93 (3)-degrees, and Z = 4. The structure was solved and refined to R = 0.036 and R(w) = 0.045 by using 3245 observed independent reflections. Comparison with the vinyl precursor clearly indicates the stronger trans influence for the acyl moiety than for the vinyl ligand.

  DOI：

  10.1021/om00039a005
• 作为产物：
  描述：

  3-甲基巴豆酰氯 、 四(三苯基膦)铂 以 甲苯 为溶剂， 以81%的产率得到(3-methylbut-2-enoyl)bis(triphenyl-l5-phosphaneyl)platinum(IV) chloride
  参考文献：
  名称：

  金属介导的乙烯基亲电子体的羰基烷氧基化反应的机理。1.乙烯基酰基铂（II）配合物的制备，分子结构和醇解

  摘要：

  The two key steps of the nickel triad metal-mediated carbalkoxylation of vinyl electrophiles were investigated using platinum complexes: (a) carbonyl insertion of sigma-vinyl Pt(II) halides and (b) alcoholysis of vinylic acyl Pt(II) complexes. NMR spectral studies suggest that the carbonyl insertion into the alkenyl C-Pt bond proceeds via the formation of a sigma-vinyl Pt(II) carbonyl species, followed by phosphine dissociation and migratory insertion. While the resulting vinylic acyl Pt(II) halides are unreactive toward alcohols, the corresponding cationic triflate complexes readily undergo alcoholysis in the absence of base. Kinetic and NMR spectral studies establish that the alcoholysis of vinylic acyl Pt(II) triflate complexes occurs via a preequilibration to form a reactive, trigonal-planar intermediate, followed by the rate-determining trans-cis isomerization and nucleophilic attack of alcohols prior to the facile reductive elimination to the alpha,beta-unsaturated carboxylic esters. Both the covalent and cationic vinylic acyl Pt(II) complexes were isolated and fully characterized. A single-crystal molecular structure determination is reported for trans-(CH3)2C = CCOPt(PPh3)2I (9b). Complex 9b crystallizes in the monoclinic space group P2(1)/n with a = 11.924 (5) angstrom, b = 20.354 (10) angstrom, c = 15.606 (7) angstrom, beta = 105.93 (3)-degrees, and Z = 4. The structure was solved and refined to R = 0.036 and R(w) = 0.045 by using 3245 observed independent reflections. Comparison with the vinyl precursor clearly indicates the stronger trans influence for the acyl moiety than for the vinyl ligand.

  DOI：

  10.1021/om00039a005