(-)-2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane radical cation | 136655-45-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (-)-2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane radical cation
• CAS: 136655-45-3
• 化学式: C₃₁H₃₂O₂P₂
• 分子量: 498.541
• InChiKey: OOAAHJGCKIDAMS-UHFFFAOYSA-N

反应信息

• 作为产物：
  描述：

  4,5-bis(diphenylphosphinomethyl)-2,2-dimethyl-1,3-dioxolane 以 二氯甲烷 为溶剂， 反应 4.0h， 生成 (-)-2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane radical cation
  参考文献：
  名称：

  Radical cations of bis(diphenylphosphino) derivatives (Ph2P-R-PPh2): the formation of localized, cyclic, and dimeric configurations; an ESR and quantum chemical study

  摘要：

  A matrix ESR study on radiogenic radical cations of Ph2P-R-PPh2 derivatives with various linkers (R) is presented. The experiments show that in a frozen dichloromethane solution the radical cations can adopt localized (Ph2PR+), cyclic (Ph2 activated P-R-PPh2.+), and dimeric (Ph2R-PRPh2+) configurations, depending on the nature of the linker. The cyclic and dimeric products are formed in the reaction of a localized cation with a second free-electron pair, resulting in an intra- or intermolecular three-electron P-P sigma* bond, respectively. The formation of the cyclic structure, with a strongly bent P-P sigma* bond, requires a specific proximate position of the two phosphine moieties in the precursor molecule. The mutual orientation of the two free-electron pairs of the precursors is assessed by NMR via the (n)J(PP) spin-spin coupling constant. Ab initio UHF quantum chemical calculations at the 3-21G*/SCF level support the assignments.

  DOI：

  10.1021/j100176a042