2,2′-bis(di-iso-propylphosphino)-trans-stilbene | 1609675-17-3

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: 2,2′-bis(di-iso-propylphosphino)-trans-stilbene
• 英文别名: [2-[(E)-2-[2-di(propan-2-yl)phosphanylphenyl]ethenyl]phenyl]-di(propan-2-yl)phosphane
• CAS: 1609675-17-3
• 化学式: C₂₆H₃₈P₂
• 分子量: 412.535
• InChiKey: JIQLZSJJVMUREO-ISLYRVAYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.5
• 重原子数：
  28
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  2,2′-bis(di-iso-propylphosphino)-trans-stilbene 以 四氢呋喃 、 氘代苯 为溶剂， 反应 4.5h， 生成 (2,2′-bis(diisopropylphosphino)-trans-stilbene)NiI
  参考文献：
  名称：

  Group 10 Metal Complexes Supported by Pincer Ligands with an Olefinic Backbone

  摘要：

  The coordination chemistry of 2,2'-bis(di-iso-propylphosphino)trans-stilbene (tPCH=CHP) with group 10 metal centers in a variety of oxidation states is reported; different coordination modes were observed depending on the oxidation state of the metal. With metal centers in the 0 or +1 oxidation state ((tPCH=CHP)Ni, [(tPCH=CHP)Pd](2), (tPCH=CHP)NiCl, (tPCH=CHP)Nil), eta(2) coordination of the olefin occurs, whereas, with metals in the +2 oxidation state, C H activation of the backbone, followed by rapid H X reductive elimination, was observed, leading to an coordination of the backbone in (tPC=CHP)MCl (M = Ni, Pd, Pt). Employing the methyl-substituted analogue, 2,2'-bis(di-iso-propylphosphino)-trans-diphenyl-1,2-dimethylethene (tPCMe=CMeP), forced an eta(2) coordination of the olefin in [(tPCMe=CMeP)NiCl](2)[NiCl4]. The synthesis of the hydride complex (tPC=CHP)NiH was attempted, but, instead, led to the formation of (tPCH=CHP)Ni, indicating that the vinyl form of the backbone can function as a hydrogen acceptor. All metal complexes were characterized by multinuclei NMR spectroscopy, X-ray crystallography, and elemental analysis.

  DOI：

  10.1021/om500256r
• 作为产物：
  描述：

  邻溴苯甲醛 在 正丁基锂 、 四氯化钛 、 锌 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 2.0h， 生成 2,2′-bis(di-iso-propylphosphino)-trans-stilbene
  参考文献：
  名称：

  Group 10 Metal Complexes Supported by Pincer Ligands with an Olefinic Backbone

  摘要：

  The coordination chemistry of 2,2'-bis(di-iso-propylphosphino)trans-stilbene (tPCH=CHP) with group 10 metal centers in a variety of oxidation states is reported; different coordination modes were observed depending on the oxidation state of the metal. With metal centers in the 0 or +1 oxidation state ((tPCH=CHP)Ni, [(tPCH=CHP)Pd](2), (tPCH=CHP)NiCl, (tPCH=CHP)Nil), eta(2) coordination of the olefin occurs, whereas, with metals in the +2 oxidation state, C H activation of the backbone, followed by rapid H X reductive elimination, was observed, leading to an coordination of the backbone in (tPC=CHP)MCl (M = Ni, Pd, Pt). Employing the methyl-substituted analogue, 2,2'-bis(di-iso-propylphosphino)-trans-diphenyl-1,2-dimethylethene (tPCMe=CMeP), forced an eta(2) coordination of the olefin in [(tPCMe=CMeP)NiCl](2)[NiCl4]. The synthesis of the hydride complex (tPC=CHP)NiH was attempted, but, instead, led to the formation of (tPCH=CHP)Ni, indicating that the vinyl form of the backbone can function as a hydrogen acceptor. All metal complexes were characterized by multinuclei NMR spectroscopy, X-ray crystallography, and elemental analysis.

  DOI：

  10.1021/om500256r

文献信息

• Coordination of a Hemilabile Pincer Ligand with an Olefinic Backbone to Mid-to-Late Transition Metals
  作者：Brittany J. Barrett、Vlad M. Iluc

  DOI：10.1021/ic500549z

  日期：2014.7.21

  mode is dependent on the oxidation state of the metal, some +2 metal complexes, (tPCH═CHP)CoCl2 and (tPCH═CHP)FeBr2, were also investigated. The coordination of the olefinic backbone is not observed in (tPCH═CHP)FeBr2, (tPCH═CHP)CoCl2, (tPCH═CHP)Cu(OTf), or [(tPCH═CHP)Ag][PF6], but η2-coordination is present in [(tPCH═CHP)CoCl][BArF4], [(tPCH═CHP)FeBr][BArF4], (tPCH═CHP)CoCl, (tPCH═CHP)CoCl(CO), (tPCH═CHP)RhCl

  中性的配位化学吨PCH═CHP钳形（吨PCH═CHP= 2,2'-双（二-异-propylphosphino） -反式-芪）与金属，在1氧化态形成稳定的络合物进行了研究，并（吨PCH═CHP）氯化钴，（吨PCH═CHP）氯化钴（CO），（吨PCH═CHP）的RhCl，（吨PCH═CHP）的Cu（OTF），[（吨PCH═CHP）的Cu] [PF 6合成和表征[（t PCHPCHP）Ag] [PF 6 ]。为了确定协调模式是否是取决于金属的氧化态，一些2的金属配合物，（吨PCH═CHP）氯化钴2还研究了（t PCHPCHP）FeBr 2。烯烃骨架的配位不（观测吨PCH═CHP）FeBr 2，（吨PCH═CHP）氯化钴2，（吨PCH═CHP）的Cu（OTF），或[（吨PCH═CHP）的Ag] [ PF 6 ]，但η 2 -coordination存在于[（吨PCH═CHP）氯化钴] [巴˚F 4
• Group 10 Metal Complexes Supported by Pincer Ligands with an Olefinic Backbone
  作者：Brittany J. Barrett、Vlad M. Iluc

  DOI：10.1021/om500256r

  日期：2014.5.27

  The coordination chemistry of 2,2'-bis(di-iso-propylphosphino)trans-stilbene (tPCH=CHP) with group 10 metal centers in a variety of oxidation states is reported; different coordination modes were observed depending on the oxidation state of the metal. With metal centers in the 0 or +1 oxidation state ((tPCH=CHP)Ni, [(tPCH=CHP)Pd](2), (tPCH=CHP)NiCl, (tPCH=CHP)Nil), eta(2) coordination of the olefin occurs, whereas, with metals in the +2 oxidation state, C H activation of the backbone, followed by rapid H X reductive elimination, was observed, leading to an coordination of the backbone in (tPC=CHP)MCl (M = Ni, Pd, Pt). Employing the methyl-substituted analogue, 2,2'-bis(di-iso-propylphosphino)-trans-diphenyl-1,2-dimethylethene (tPCMe=CMeP), forced an eta(2) coordination of the olefin in [(tPCMe=CMeP)NiCl](2)[NiCl4]. The synthesis of the hydride complex (tPC=CHP)NiH was attempted, but, instead, led to the formation of (tPCH=CHP)Ni, indicating that the vinyl form of the backbone can function as a hydrogen acceptor. All metal complexes were characterized by multinuclei NMR spectroscopy, X-ray crystallography, and elemental analysis.