triphenylphosphine radical cation

• 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: triphenylphosphine radical cation
• 英文别名: Triphenylphosphin-Radikalkation；TPP⁺
• 化学式: C₁₈H₁₅P
• 分子量: 262.291
• InChiKey: LGYHWACMXJEPAO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 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：

  triphenylphosphine radical cation 在 air 作用下， 以 乙腈 为溶剂， 生成
  参考文献：
  名称：

  三芳基膦自由基阳离子与氧反应过程中取代基对芳基的影响。

  摘要：

  在先前的报告（S. Yasui，S。Tojo和T. Majima，J。Org。Chem。，2005，70，1276）中，我们介绍了激光闪光光解（LFP）的结果以及对这9种产品的分析。空气中乙腈中的10-二氰基蒽（DCA）光敏氧化三芳基膦（Ar（3）P），表明光反应导致Ar（3）P氧化，得到相应的氧化膦（Ar（3）P = O）的收率几乎是定量的，并且该反应是由电子（ET）从Ar（3）P到单重激发态（（1）DCA *）的DCA转移而引发的，从而生成三芳基膦自由基阳离子Ar（ 3）P（+）。该自由基阳离子通过与O（2）的自由基偶合而衰减，从而提供过氧自由基阳离子Ar（3）P（+）-OO *，我们建议将其作为导致产物Ar（3）P = O的中间体。现在，我们使用十种具有各种电子和空间特性的Ar（3）P更详细地研究了这种光反应。通过LFP测量的Ar（3）P *（+）的衰减速率仅受Ar（3）P芳基上的取

  DOI：

  10.1039/b606857j
• 作为产物：
  描述：

  三苯基膦 以 various solvent(s) 为溶剂， 生成 triphenylphosphine radical cation
  参考文献：
  名称：

  三电子σ键自由基：氟利昂中R 3 P-Cl自由基的电子顺磁共振光谱研究

  摘要：

  我们的主要目的是要提请注意的三电子的相对稳定性σ键合的基团（σ 2 1，σ 1 2），大量的这种基团的已被研究了EPR spectroscopists，以及它们作为反应中间体的潜在重要性。该主题由实验其显示是当R所示3 P ˙+自由基阳离子（ME 3 P ˙+且Ph 3 P ˙+ ）以产生CFCL 3在77K通过暴露于60条钴γ射线，并且该系统退火到大约在155 K下，检测到具有R 3 P [Cl]基团的特征，并与31 P和35/37 Cl核定义良好的超精细偶联。认为这些一定是由电子捕获后从（CFCl 3）˙-自由基阴离子释放的氯离子形成的。

  DOI：

  10.1039/ft9908603293
• 作为试剂：
  描述：

  7-diphenylmethylene-2,3-benzonorbornadiene 在 氧气 、 triphenylphosphine radical cation 作用下， 以 二氯甲烷 为溶剂， 以30%的产率得到3,3-diphenylnaphtho[1,2-c]furan-1(3H)-one
  参考文献：
  名称：

  摘要：

  The crystal structure of 3, 3-diphenylnaphtho[1, 2-c]furan-1(3H)-one 2 was determined by X-ray diffraction analysis. It possesses P2(1)2(1)2(1) (#19) space group symmetry, with a = 11.922(2), b = 17.142(4), c = 8.429(2) Angstrom, and D-calc = 1.297 mg/m(3) for Z = 4.

  DOI：

  10.1023/a:1009561909291

文献信息

• Preparation and structure of certain phosphorus-centred radical cations. An electron spin resonance study
  作者：Akinori Hasegawa、Glen D. G. McConnachie、Martyn C. R. Symons

  DOI：10.1039/f19848001005

  日期：——

  60Co γ-rays at 77 K gave the corresponding cations, [·PL3]+, characterised by their e.s.r. spectra. The spectra establish that the SOMO for these cations is considerably localised on phosphorus, which contributes extensive atomic 3s and 3p character. The results confirm and extend previous studies using sulphuric acid matrices. The tendency for these cations to react with corresponding neutral molecules

  各种三价磷衍生物的稀溶液，PL的曝光3，在fluorotri氯甲烷到60个钴γ射线在77K，得到相应的阳离子，[·PL 3 ] +，其特征在于可以通过ESR光谱。光谱表明，这些阳离子的SOMO相当局限在磷上，这贡献了广泛的3 s和3 p原子特性。结果证实并扩展了以前使用硫酸基质的研究。这些阳离子与相应的中性分子反应以生成σ *二聚阳离子的趋势[L 3 P [图形省略] PL 3 ]+也被确认。
• Reaction of Triarylphosphine Radical Cations Generated from Photoinduced Electron Transfer in the Presence of Oxygen
  作者：Shinro Yasui、Sachiko Tojo、Tetsuro Majima

  DOI：10.1021/jo049032l

  日期：2005.2.1

  The 9,10-dicyanoanthracene (DCA)-sensitized photoreaction of triarylphosphines (1) was carried out in acetonitrile under aerobic conditions. Phosphine 1 was oxidized to the corresponding phosphine oxide with no appreciable side reactions. Product analysis and laser flash photolysis experiments suggest that the radical cation of 1 formed by the electron transfer from 1 to DCA in the singlet excited

  在有氧条件下在乙腈中进行三芳基膦（1）的9,10-二氰基蒽（DCA）致敏的光反应。将膦1氧化为相应的氧化膦，没有明显的副反应。产物分析和激光闪光光解实验表明，由单重激发态的电子从1转移到DCA（1 DCA *）形成的1的自由基阳离子与O 2反应，最终得到氧化膦。
• Radiolytic Studies of the Mechanism of Autoxidation of Triphenylphosphine and Related Compounds
  作者：Z. B. Alfassi、P. Neta、Bruce Beaver

  DOI：10.1021/jp9637486

  日期：1997.3.1

  Triphenylphosphine (Ph(3)P) undergoes one-electron oxidation in irradiated CH2Cl2 solutions to yield the radical cation Ph(3)P(.+). This short-lived species exhibits intense absorption with a maximum at 325 nm and an extended shoulder at 400-500 nm and decays by a second-order process in the absence of O-2. In the presence of O-2, however, the radical cation reacts with O-2 with a rate constant of 7 x 10(6) L mol(-1) s(-1) to yield a peroxyl radical, Ph(3)P(+)OO(.), which exhibits no significant absorbance at lambda > 300 nm. Similar results, but with slightly different rate constants, were obtained also in CCl4 solutions and in CH3CN and cyclohexane solutions containing 1% CCl4. Tris(2,4,6-trimethoxyphenyl)phosphine in CH2Cl2 exhibits a behavior similar to that of Ph(3)P, but the reaction of its radical cation with O-2 is an order of magnitude more rapid. On the other hand, the perfluorinated Ph(3)P(.+) in CH2Cl2 reacts with O-2 much more slowly, if at all. Diphenyl-2-pyridylphosphine yields a radical cation which exhibits a slightly narrower absorption band but reacts with O-2 With the same rate constant as Ph(3)P(.+). The peroxyl radicals propagate a chain reaction by further oxidation of phosphine molecules to Ph(3)P(.+) either directly or indirectly. The final radiolysis product is the phosphine oxide, Ph(3)PO. The radiolytic yields for oxidation of the phosphines were much higher than the radiolytic yield of the solvent derived radicals, except for the case of the perfluoro derivative, and were dependent on the concentrations of phosphine and O-2 and on the dose rate. At low dose rates and high solute concentrations the chain lengths exceeded 1000.
• Reactivity of Triarylphosphine Peroxyl Radical Cations Generated through the Reaction of Triarylphosphine Radical Cations with Oxygen
  作者：Sachiko Tojo、Shinro Yasui、Mamoru Fujitsuka、Tetsuro Majima

  DOI：10.1021/jo061319q

  日期：2006.10.1

  One-electron oxidation of triarylphosphines (Ar3P, Ar = phenyl and substituted phenyl) in benzonitrile (PhCN) has been studied using pulse radiolysis technique. One-electron oxidation of Ar3P occurred to yield the radical cation (Ar3P center dot+) which showed an intense absorption with a peak at 360-370 nm together with a broad band at 500-600 nm. The addition of molecular oxygen (O-2) to the phosphorus atom of Ar3P center dot+ took place at the second-order rate constant of 10(7)-10(9) dm(3) mol(-1) s(-1) to yield the peroxyl triarylphosphinyl radical cation ((Ar3P+OO center dot)). It is found that the electron-releasing substituents on the para position of the phenyl ring of Ar3P influence the rate constants of the reaction of Ar3P center dot+ with O-2 and that o-methyl substituents on the phenyl ring influence the reactivity of (Ar3P+OO center dot).
• Effects of substituents on aryl groups during the reaction of triarylphosphine radical cation and oxygen
  作者：Shinro Yasui、Sachiko Tojo、Tetsuro Majima

  DOI：10.1039/b606857j

  日期：——

  electron transfer (ET) from Ar(3)P to DCA in the singlet excited state ((1)DCA*), producing the triarylphosphine radical cation Ar(3)P (+). This radical cation decays through radical coupling with O(2) to afford the peroxy radical cation Ar(3)P(+)-O-O*, which we proposed to be the intermediate leading to the product Ar(3)P=O. We now examined this photoreaction in more detail using ten kinds of Ar(3)P

  在先前的报告（S. Yasui，S。Tojo和T. Majima，J。Org。Chem。，2005，70，1276）中，我们介绍了激光闪光光解（LFP）的结果以及对这9种产品的分析。空气中乙腈中的10-二氰基蒽（DCA）光敏氧化三芳基膦（Ar（3）P），表明光反应导致Ar（3）P氧化，得到相应的氧化膦（Ar（3）P = O）的收率几乎是定量的，并且该反应是由电子（ET）从Ar（3）P到单重激发态（（1）DCA *）的DCA转移而引发的，从而生成三芳基膦自由基阳离子Ar（ 3）P（+）。该自由基阳离子通过与O（2）的自由基偶合而衰减，从而提供过氧自由基阳离子Ar（3）P（+）-OO *，我们建议将其作为导致产物Ar（3）P = O的中间体。现在，我们使用十种具有各种电子和空间特性的Ar（3）P更详细地研究了这种光反应。通过LFP测量的Ar（3）P *（+）的衰减速率仅受Ar（3）P芳基上的取