Phenylnitrene Radical Cation Rearrangements,The Journal of Physical Chemistry A

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Phenylnitrene Radical Cation Rearrangements
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2018-10-09 00:00:00 , DOI: 10.1021/acs.jpca.8b08480
Didier Bégué ₁ , Alain Dargelos ₁ , Curt Wentrup ₂

Affiliation

The electronic structure and the rearrangements of the phenylnitrene radical cation C₆H₅N^.+2^.+ have been investigated at DFT and CASPT2(7,9) levels of theory. The ²B₂ state has the lowest energy of five identified electronic states, and it can undergo ring expansion to the 1-azacycloheptetetraene radical cation 4^.+ with an activation energy of ca. 28 kcal/mol. Ring opening and recyclization provide a route to 5-cyanocyclopentadiene radical cation 8^.+, which may undergo facile 1,5-hydrogen shifts. The 2-, 3-, and 4-pyridylcarbene radical cations 31^.+, 35^.+ , and 39^.+ interconvert with the phenylnitrene radical cation via azacycloheptatetraenes with activation barriers <35 kcal/mol. The carbene–carbene and carbene–nitrene rearrangements, ring expansions, ring contractions, ring openings (e.g., to cyanopentadienylidene 28^.+), and cyclizations taking place in all these radical cations are completely analogous to the thermal and photochemical rearrangements.

中文翻译：

苯硝烯自由基阳离子重排

在DFT和CASPT2（7,9）的理论水平上研究了亚苯基亚苯基自由基阳离子C ₆ H ₅ N。⁺2。⁺的电子结构和重排。的²乙₂状态具有五个识别电子态的最低能量，并且它可以进行环扩展到1-azacycloheptetetraene自由基阳离子4 ⁺用约的活化能 28 kcal / mol。开环和环化提供了通往5-氰基环戊二烯自由基阳离子8。⁺的途径，该途径可能会发生容易的1,5-氢转移。2-，3-和4-吡啶基碳烯自由基阳离子31 ^。+，35⁺和39。⁺通过活化障碍<35 kcal / mol的氮杂环庚七烯与苯基亚硝基自由基阳离子互变。在所有这些自由基阳离子中发生的卡宾-卡宾和卡宾-氮烯重排，环膨胀，环收缩，环开口（例如，生成氰基戊二烯基28。⁺）和环化与热和光化学重排完全相似。

更新日期：2018-10-09

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