直接的
指示
化学
离子键合
芳香性
阳离子聚合
计算化学
耦合簇
亚胺离子
离子
立体化学
药物化学
分子
有机化学
原子物理学
物理
激发态
单重态
作者
Dominic A. Sirianni,Xinli Song,Salmika Wairegi,Evan B. Wang,Sebastian A Mendoza-Gomez,Adam Luxon,Maxwell Zimmerley,Ariana Nussdorf,Michael Filatov,Roald Hoffmann,Carol A. Parish
摘要
The Bergman cyclization of (Z)-hexa-3-ene-1,5-diyne to form the aromatic diradical p-benzyne has garnered attention as a potential antitumor agent due to its relatively low cyclization barrier and the stability of the resulting diradical. Here, we present a theoretical investigation of several ionic extensions of the fundamental Bergman cyclization: electrocyclizations of the penta-1,4-diyne anion, hepta-1,6-diyne cation, and octa-1,7-diyne dication, leveraging the spin-flip formulation of the equation-of-motion coupled cluster theory with single and double substitutions (EOM-SF-CCSD). Though the penta-1,4-diyne anion exhibits a large cyclization barrier of +66 kcal mol-1, cyclization of both the hepta-1,6-diyne cation and octa-1,7-diyne dication along a previously unreported triplet pathway requires relatively low energy. We also identified the presence of significant aromaticity in the triplet diradical products of these two cationic cyclizations.
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