Brotsman Victor A, Troyanov Sergey I
Chemistry Department, Moscow State University, Leninskie gory, 119991 Moscow, Russia.
Inorg Chem. 2024 Jan 8;63(1):548-553. doi: 10.1021/acs.inorgchem.3c03447. Epub 2023 Dec 16.
Fullerene C contains two isomers obeying the Isolated-Pentagon Rule (IPR), -C(16) and -C(17). Both isomers undergo unprecedented skeletal transformations at high-temperature (400 °C) chlorination with SbCl. One-step Stone-Wales rearrangement (SWR) in C(17) results in the pentagon-fused C cage found in the structure of CCl. CF derivatives with the same cage, two isomers of C(CF) and C(CF)O, were obtained by high-temperature trifluoromethylation of the chlorination products with CFI, followed by HPLC separation. The skeletal transformation of C(16) proceeds via two SWRs under the formation of a C cage with one fused-pentagon pair found in the structure of C(CF). The addition patterns in skeletally transformed molecules are discussed in detail, disclosing the influence of the pentagon fusions, isolated C=C bonds, and benzenoid rings on the stability of the molecules with non-IPR C cages. The chlorination-promoted SWRs in C isomers have been observed for the first time, which contribute a lot to the understanding of skeletal transformations in fullerenes.
富勒烯C包含两种遵循孤立五边形规则（IPR）的异构体，即-C(16)和-C(17)。两种异构体在高温（400℃）下与SbCl进行氯化反应时都会发生前所未有的骨架转变。C(17)中的一步斯通-威尔士重排（SWR）会产生在CCl结构中发现的五边形稠合C笼。通过用CFI对氯化产物进行高温三氟甲基化，然后进行HPLC分离，得到了具有相同笼结构的CF衍生物，即C(CF)和C(CF)O的两种异构体。C(16)的骨架转变通过两次SWR进行，形成了在C(CF)结构中发现的具有一对稠合五边形的C笼。详细讨论了骨架转变分子中的加成模式，揭示了五边形稠合、孤立的C=C键和苯环对具有非IPR C笼的分子稳定性的影响。首次观察到C异构体中氯化促进的SWR，这对理解富勒烯中的骨架转变有很大帮助。
