1,3-cyclopentadiyl biradical | 56564-28-4

• 分子结构分类: 有机化合物 - 有机盐
• 英文名称: 1,3-cyclopentadiyl biradical
• 英文别名: cyclopentane-1,3-diyl；1,3-cyclopentanediyl；1,3-Cyclopentandiyl；1,3-cyclopentadiyl；1,3-Cyclopentadienyl-diradikal；1,3-Cyclopentadiyl-Diradikal；cyclopentane
• CAS: 56564-28-4
• 化学式: C₅H₈
• 分子量: 68.1185
• InChiKey: VSSLJIAEWINZCT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  5
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 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：

  1,3-cyclopentadiyl biradical 在 二苯甲酮 、 氧气 作用下， 以 四氯化碳 为溶剂， 生成 2,3-dioxabicyclo<2.2.1>heptane
  参考文献：
  名称：

  紫外激光光化学：三线态双自由基捕获效率和寿命

  摘要：

  三线态 1,3-环戊二基 (1) 和三线态 1,4-双基 2-(2-乙基) 环戊-2-烯基 (2) 与分子氧的捕获已进行了定量研究。已发现 1 的寿命在 720 到 900 ns 之间，而 2 的寿命在 53 到 94 ns 之间，具体取决于溶剂。发现双自由基 1 以基本上定量的产率被捕获，没有氧催化系统间交叉的迹象。相比之下，发现 2 以 54-79% 的产率被捕获，残留的双自由基猝灭是由于氧催化的系统间交叉。这些和其他双自由基捕获数据已与 1,3-双自由基几何相关联，并且发现符合塞勒姆关于三重双自由基中自旋轨道耦合的规则。28 篇参考文献、7 幅图、2 张表格。

  DOI：

  10.1021/ja00265a015
• 作为产物：
  描述：

  5,6-二氮杂双环[2.2.1]庚-5-烯 在 二苯甲酮 作用下， 以 乙腈 为溶剂， 生成 1,3-cyclopentadiyl biradical
  参考文献：
  名称：

  Determination of the triplet lifetimes of 1,3-cyclopentanediyl biradicals derived from the photodenitrogenation of azoalkanes with time-resolved photoacoustic calorimetry

  摘要：

  The triplet lifetime of the parent 1,3-cyclopentanediyl (2a) and the 4-methylene and the 1-phenyl derivatives 2b and 2c were determined by time-resolved photoacoustic calorimetry (PAC). For the biradical 2b, PAC was the only suitable method to date for determining its hitherto inaccessible triplet lifetime. A comparison with results for biradicals 2a,c obtained in earlier studies shows that PAC is a reliable method for measuring triplet lifetimes of biradicals. The effect on the triplet lifetimes of allyl and benzyl conjugation at one radical center in 2b,c proved to be insignificant. In view of the large enhancement of the biradical lifetime as the result of benzylic conjugation at both radical sites, as in the diphenyl derivative 2d, the present results imply that the biradicals 2b,c are still flexible enough to enable effective intersystem crossing through pyramidalization. The much larger (ca. 200-fold) triplet lifetime of biradical 2b compared to its gem-dimethyl derivative 2e suggests that geminal substitution is a general phenomenon for the effective reduction of the lifetimes of triplet biradicals through changes in the singlet-triplet energy gap.

  DOI：

  10.1021/jo00058a031

文献信息

• Time-resolved infrared studies of triplet 1,3-cyclopentanediyl
  作者：Brett M. Showalter、Timothy C. Bentz、Lev R. Ryzhkov、Christopher M. Hadad、John P. Toscano

  DOI：10.1002/1099-1395(200006)13:6<309::aid-poc242>3.0.co;2-a

  日期：2000.6

  acetonitrile-d3 solutions results in the formation of bicyclo[2.1.0]pentane (3), a ring closure product arising from an intermediate 1,3-cyclopentanediyl triplet biradical (2). Time-resolved infrared (TRIR) spectroscopy was used to monitor the kinetics of bicyclopentane 3 production. This analysis provides a measurement of the triplet biradical lifetime and an estimate of the bimolecular reaction rate between

  2,3-二氮杂双环[2.2.1]hept-2-ene (1) 在氩或氧饱和的乙腈-d3 溶液中的三重态光解导致双环[2.1.0]戊烷 (3) 的形成，由中间体 1,3-环戊二基三联双自由基 (2) 产生的闭环产物。时间分辨红外 (TRIR) 光谱用于监测双环戊烷 3 生产的动力学。该分析提供了三重态双自由基寿命的测量和双自由基 2 与氧之间的双分子反应速率的估计，两者都与先前的研究非常一致。我们的研究还表明，由于 3 在 C-H 拉伸区域中的某些 IR 带与双自由基 2 中的相应带重叠。这种解释得到了计算调查的支持。版权所有 © 2000 John Wiley & Sons, Ltd.
• The experimental heats of formation and kinetics of 1,3-biradicals using time-resolved photoacoustic calorimetry
  作者：Michael S. Herman、Joshua L. Goodman

  DOI：10.1021/ja00216a069

  日期：1988.4

  Utilisation de la calorimetrie photoacoustique pour mesurer directement les chaleurs de formation et la cinetique de 2 biradicaux: cyclopentanediyl-1,3 et isopropylidene-2 cyclopentanediyl-1,3

  使用 de la calorimetrie photoacoustique pour mesurer directement les chaleurs de形成等 la cinetique de 2 biradicaux: cyclopentanediyl-1,3 et isopropylidene-2 cyclopentanediyl-1,3
• Adam, Waldemar; Hannemann, Klaus; Wilson, R. Marshall, Angewandte Chemie, 1985, vol. 97, # 12, p. 1072 - 1073
  作者：Adam, Waldemar、Hannemann, Klaus、Wilson, R. Marshall

  DOI：——

  日期：——
• Determination of the triplet lifetimes of 1,3-cyclopentanediyl biradicals derived from the photodenitrogenation of azoalkanes with time-resolved photoacoustic calorimetry
  作者：Waldemar Adam、Herbert Platsch、Juergen Sendelbach、Jakob Wirz

  DOI：10.1021/jo00058a031

  日期：1993.3

  The triplet lifetime of the parent 1,3-cyclopentanediyl (2a) and the 4-methylene and the 1-phenyl derivatives 2b and 2c were determined by time-resolved photoacoustic calorimetry (PAC). For the biradical 2b, PAC was the only suitable method to date for determining its hitherto inaccessible triplet lifetime. A comparison with results for biradicals 2a,c obtained in earlier studies shows that PAC is a reliable method for measuring triplet lifetimes of biradicals. The effect on the triplet lifetimes of allyl and benzyl conjugation at one radical center in 2b,c proved to be insignificant. In view of the large enhancement of the biradical lifetime as the result of benzylic conjugation at both radical sites, as in the diphenyl derivative 2d, the present results imply that the biradicals 2b,c are still flexible enough to enable effective intersystem crossing through pyramidalization. The much larger (ca. 200-fold) triplet lifetime of biradical 2b compared to its gem-dimethyl derivative 2e suggests that geminal substitution is a general phenomenon for the effective reduction of the lifetimes of triplet biradicals through changes in the singlet-triplet energy gap.
• UV laser photochemistry: triplet biradical trapping efficiencies and lifetimes
  作者：Waldemar. Adam、Klaus. Hannemann、R. Marshall. Wilson

  DOI：10.1021/ja00265a015

  日期：1986.3

  been studied quantitatively. The lifetime of 1 has been found to range between 720 and 900 ns and that of 2 between 53 and 94 ns depending on the solvent. The biradical 1 was found to be trapped in essentially quantitative yield with no indication of oxygen-catalyzed intersystem crossing. In contrast, 2 was found to be trapped in 54-79% yield with the residual biradical quenching being due to oxygen-catalyzed

  三线态 1,3-环戊二基 (1) 和三线态 1,4-双基 2-(2-乙基) 环戊-2-烯基 (2) 与分子氧的捕获已进行了定量研究。已发现 1 的寿命在 720 到 900 ns 之间，而 2 的寿命在 53 到 94 ns 之间，具体取决于溶剂。发现双自由基 1 以基本上定量的产率被捕获，没有氧催化系统间交叉的迹象。相比之下，发现 2 以 54-79% 的产率被捕获，残留的双自由基猝灭是由于氧催化的系统间交叉。这些和其他双自由基捕获数据已与 1,3-双自由基几何相关联，并且发现符合塞勒姆关于三重双自由基中自旋轨道耦合的规则。28 篇参考文献、7 幅图、2 张表格。