Dimerization of indenocorannulene radicals: imposing stability through increasing strain and curvature
Dimerization of indenocorannulene radicals: imposing stability through increasing strain and curvature
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茚并环烯自由基的二聚化：通过增加应变和曲率来增强稳定性
DOI：
10.1039/d0qo00686f
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发表时间：
2020
影响因子：
5.4
通讯作者：
Petrukhina, Marina A.
中科院分区：
文献类型：
--
作者：
Rogachev, Andrey Yu.;Zhu, Yikun;Zhou, Zheng;Liu, Shuyang;Wei, Zheng;Petrukhina, Marina A.
碗状茚并轮烯C26 H12在THF中与Rb金属单电子还原得到[{Rb+（18-crown-6）}2（C26 H12-C26 H12）2-]·4THF，单晶X射线衍射证实。该产物由一个二聚体σ-键合的二价阴离子（C-C，1.568（7）Rb）和两个内η6配位的{Rb+（18-冠-6）}基团（Rb-C，3.272（4）-3.561（4）Rb）组成。（C26 H12-C26 H12）2−二聚体代表了第一个晶体学证实的茚并corannulene单阴离子自由基C26 H12 stec −自发偶联的例子。对新二聚体的全面理论研究证实了接头的单一σ键特征，并揭示了与由诸如corannulene及其二苯并衍生物等π碗形成的类似物相比，[σ-（C26 H12）2]2−的热力学和动力学稳定性显著增加。深入的计算分析和系列的直接比较证明了曲率对自由基耦合过程的影响，允许控制碗状π-自由基的稳定性和反应性。
One-electron reduction of bowl-shaped indenocorannulene, C26H12, with Rb metal in THF affords [{Rb+(18-crown-6)}2(C26H12–C26H12)2−]·4THF, as confirmed by single-crystal X-ray diffraction. The product consists of a dimeric σ-bonded dianion (C–C, 1.568(7) Å) having two endo-η6 coordinated {Rb+(18-crown-6)} moieties (Rb–C, 3.272(4)–3.561(4) Å). The (C26H12–C26H12)2− dimer represents the first crystallographically confirmed example of spontaneous coupling for indenocorannulene monoanion radicals, C26H12˙−. Comprehensive theoretical investigation of the new dimer confirms the single σ-bond character of the linker and reveals a significant increase of both thermodynamic and kinetic stability of [σ-(C26H12)2]2− in comparison with analogues formed by such π-bowls as corannulene and its dibenzo-derivative. The in-depth computational analysis and direct comparison of the series demonstrates the effect of curvature on radical coupling processes, allowing control over stability and reactivity of bowl-shaped π-radicals.
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