benzyl(cycloocta-1,5-diene)(neophyl)platinum(II) | 141439-23-8

• 英文名称: benzyl(cycloocta-1,5-diene)(neophyl)platinum(II)
• CAS: 141439-23-8
• 化学式: C₂₅H₃₂Pt
• 分子量: 527.609
• InChiKey: YNDQGICMXBOUTO-ONEVTFJLSA-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：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  benzyl(cycloocta-1,5-diene)(neophyl)platinum(II) 、 1,2-双(二苯基膦)乙烷 以 甲苯 为溶剂， 以89%的产率得到benzyl{bis(1,2-diphenylphosphino)ethane}(neophyl)platinum(II)
  参考文献：
  名称：

  [双（二苯基膦基）乙烷]双（新叶）铂（II）的热解和光解重排的机理研究

  摘要：

  Comparative mechanistic studies are presented of the thermolytic and photolytic behavior of the bis-(neophyl)platinum(II) derivative Pt(CH2CMe2Ph)2(dppe) (neophyl = 2-methyl-2-phenylpropyl; dppe = 1,2-bis(diphenylphosphino)ethane). Thermolytic rearrangement is less facile than for monodentate P-donor analogues and affords the platinaindan Pt(2-C6H4CMe2CH2)(dppe) by intramolecular aromatic C-H activation and H-transfer to eliminated tert-butylbenzene. The kinetic isotope effect on metallacyclization (k(obs)H/k(obs)D = 2.40) and the negative activation entropy (DELTA-S(double dagger)obs = -13 (+/-4) J.K-1.mol-1) suggest a pathway in which scission of one Pt-P is mechanistically significant but C-H addition to Pt has the most energetic transition state. Photolytic rearrangement in toluene-d0 proceeds by two major paths, both of which involve primary Pt-C homolysis. The resultant neophyl radical may then provide a destination for migrating hydrogen in a cyclometalation of the residual 17-electron organoplatinum species, leading to Pt(2-C6H4CMe2CH2) (dppe). Alternatively, H-abstraction by the neophyl fragment within the solvent cage produces a benzyl radical which recombines with the metal moiety to give Pt(CH2Ph)(CH2Me2Ph)(dppe). This benzylplatinum complex is also photolabile, giving ultimately platinaindan via benzyl radical expulsion. This "indirect' solvent metalation is not evident during photolysis in toluene-d8 and in benzene.

  DOI：

  10.1021/om00043a049
• 作为产物：
  描述：

  [(1,5-cyclooctadiene)Pt(neophenyl)Cl] 、 苄基溴化镁 以 乙醚 为溶剂， 以78%的产率得到benzyl(cycloocta-1,5-diene)(neophyl)platinum(II)
  参考文献：
  名称：

  [双（二苯基膦基）乙烷]双（新叶）铂（II）的热解和光解重排的机理研究

  摘要：

  Comparative mechanistic studies are presented of the thermolytic and photolytic behavior of the bis-(neophyl)platinum(II) derivative Pt(CH2CMe2Ph)2(dppe) (neophyl = 2-methyl-2-phenylpropyl; dppe = 1,2-bis(diphenylphosphino)ethane). Thermolytic rearrangement is less facile than for monodentate P-donor analogues and affords the platinaindan Pt(2-C6H4CMe2CH2)(dppe) by intramolecular aromatic C-H activation and H-transfer to eliminated tert-butylbenzene. The kinetic isotope effect on metallacyclization (k(obs)H/k(obs)D = 2.40) and the negative activation entropy (DELTA-S(double dagger)obs = -13 (+/-4) J.K-1.mol-1) suggest a pathway in which scission of one Pt-P is mechanistically significant but C-H addition to Pt has the most energetic transition state. Photolytic rearrangement in toluene-d0 proceeds by two major paths, both of which involve primary Pt-C homolysis. The resultant neophyl radical may then provide a destination for migrating hydrogen in a cyclometalation of the residual 17-electron organoplatinum species, leading to Pt(2-C6H4CMe2CH2) (dppe). Alternatively, H-abstraction by the neophyl fragment within the solvent cage produces a benzyl radical which recombines with the metal moiety to give Pt(CH2Ph)(CH2Me2Ph)(dppe). This benzylplatinum complex is also photolabile, giving ultimately platinaindan via benzyl radical expulsion. This "indirect' solvent metalation is not evident during photolysis in toluene-d8 and in benzene.

  DOI：

  10.1021/om00043a049