Reactivity of the 3,4,5-Tridehydropyridinium Cation - Aromatic σ,σ,σ-Triradical
Reactivity of the 3,4,5-Tridehydropyridinium Cation - Aromatic σ,σ,σ-Triradical
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DOI：
10.1002/anie.200802714
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发表时间：
2008-01-01
影响因子：
16.6
通讯作者：
Kenttamaa, Hilkka I.
中科院分区：
文献类型：
--
作者：
Jankiewicz, Bartlomiej J.;Reece, Jennifer N.;Kenttamaa, Hilkka I.
以芳族碳为中心的σ，σ，σ-三自由基（1-3）已成为最近几项研究的主题。[1-8]理论研究[1-4]已经预测2A 1态是1，3，5-三脱氢苯（3）的基态。1，2，3-三脱氢苯（1）的基态最初被指定为[2b，c] 2B 2，但后来的实验和理论研究[6，7]表明基态实际上是2A 1，2B 2态的能量高出约1-2 kcal molecular 1。研究最少的异构体1，2，4-三脱氢苯（2）被预测[2c]具有2A'基态。已报道的少数研究包括对1，3，5-三脱氢苯（3）[1]的热化学测量和对1，2，3-三脱氢苯（1）[6]和全氟-1，3，5-三脱氢苯的红外检测的基质分离。[5]最近，我们报道了[8]对相关的σ，σ，σ-三自由基，2，4，6-三脱氢吡啶阳离子（4）的首次反应性研究。
Aromatic carbon-centered σ, σ, σ-triradicals (1–3) have been the subject of several recent studies.[1–8] Theoretical studies [1–4] have predicted that the 2A1 state is the ground state for 1, 3, 5-tridehydrobenzene (3). The ground state of 1, 2, 3-tridehydrobenzene (1) was initially assigned [2b, c] to be 2B2, but later experimental and theoretical studies [6, 7] showed that the ground state is actually 2A1, with the 2B2 state lying about 1–2 kcal molÀ1 higher in energy. The least studied isomer, 1, 2, 4-tridehydrobenzene (2), has been predicted [2c] to have a 2A’ground state.Experimental data for the tridehydrobenzenes are limited. The few studies that have been reported include thermochemical measurements on 1, 3, 5-tridehydrobenzene (3)[1] and matrix isolation with IR detection of 1, 2, 3-tridehydrobenzene (1)[6] and perfluoro-1, 3, 5-tridehydrobenzene.[5] Recently, we reported [8] the first reactivity study on a related σ, σ, σ-triradical, the 2, 4, 6-tridehydropyridinium cation (4).