Lyakhovetsky Yuri I, Pleshkova Alexandra P, Shilova Elena A, Ponomareva Tatyana V, Gasanov Rashid G, Tumanskii Boris L, Borisov Yuri A, Nekrasov Yuri S
A.N. Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences, 28 Vavilov St., 119991 GSP-1 Moscow V-334, Russia.
Eur J Mass Spectrom (Chichester). 2012;18(4):361-76. doi: 10.1255/ejms.1190.
C(60) was reacted in the ionization chamber of a mass spectrometer under electron impact (EI) with aldehydes, RCHO (R = Ph, p-FC(6)H(4), F(5)C(6), p-MeOC(6)H(4), α-thienyl, o-HOC(6)H(4), o-BrC(6)H(4), m-BrC(6)H(4) and t-Bu), with the transfer of R• radicals and with Me•-transfer from i-PrCHO and t-BuCHO. Paramagnetic fullerene derivatives were stabilized by the addition of the next R• radical or a hydrogen atom, or hydrogen or bromine atom loss. A detailed study showed that the reaction between C(60) and PhCHO occurred via a homolytic mechanism that matches one reported earlier for the reaction with acetone. This suggests the generality of the mechanism for the reactions of fullerenes with other species in ionization chambers under EI at ca 300°C. All aldehydes, except one, had radicals at the carbonyl group which were different from those in the ketones examined earlier in the reactions. This expanded the variety of radicals which can be transferred to fullerenes during reactions in ionization chambers under EI. Due to this and the hydrogen atom at the CO group of aldehydes, some reactions occurred that were not found for the ketones: the formation of cyclic products C(60)COC(6)H(4) and C(60)OC(6)H(4) for PhCHO, o-BrC(6)H(4)CHO and o-HOC(6)H(4)CHO, respectively, and HC(60)Ph for o- and m-BrC(6)H(4)CHO. The reaction with α- formylthiophen gives the first example of transferring an aromatic heterocyclic radical to C(60) in an ionization chamber under EI. C(70) reacted with PhCHO, p-FC(6)H(4)CHO and i- PrCHO similarly to C(60). The results for the reactions of C(60) with PhCHO and with i- PrCHO were compared with those in solution under UV irradiation. Incomplete but reasonable coincidence was found; in both modes, the addition of Ph•, PhCO• and Me• radicals to C(60) occurred, whereas some other products were formed in solution, and the explanation is given as to why this occurred. This conformity supports the hypothesis based on the results of kindred reactions with ketones and organomercurials: the results of EI-initiated homolytic reactions between fullerenes and other compounds in an ionization chamber can predict the reactivity of the fullerenes toward them in solution.
C(60) 在质谱仪的电离室中于电子轰击（EI）条件下与醛类 RCHO（R = 苯基、对氟苯基、五氟苯基、对甲氧基苯基、α-噻吩基、邻羟基苯基、邻溴苯基、间溴苯基和叔丁基）反应，会发生 R• 自由基的转移以及异丙醛和叔丁醛中 Me• 的转移。顺磁性富勒烯衍生物通过添加下一个 R• 自由基或氢原子，或者通过氢原子或溴原子的损失而得以稳定。详细研究表明，C(60) 与苯甲醛的反应通过一种均裂机制进行，该机制与先前报道的与丙酮反应的机制相匹配。这表明在约 300°C 的 EI 条件下，富勒烯在电离室中与其他物质反应的机制具有普遍性。除一种醛外，所有醛在羰基处的自由基与先前在酮类反应中检测到的自由基不同。这增加了在 EI 条件下电离室反应过程中可转移至富勒烯的自由基种类。由于此点以及醛类 CO 基团上的氢原子，发生了一些酮类反应中未发现的反应：分别由苯甲醛、邻溴苯甲醛和邻羟基苯甲醛形成环状产物 C(60)COC(6)H(4) 和 C(60)OC(6)H(4)，以及由邻溴苯甲醛和间溴苯甲醛形成 HC(60)Ph。与 α-甲酰基噻吩的反应给出了在 EI 条件下电离室中芳香族杂环自由基转移至 C(60) 的首个实例。C(70) 与苯甲醛、对氟苯甲醛和异丙醛的反应与 C(60) 类似。将 C(60) 与苯甲醛和异丙醛反应的结果与紫外光照射下溶液中的反应结果进行了比较。发现了不完全但合理的一致性；在两种模式下，均发生了 Ph•、PhCO• 和 Me• 自由基加成至 C(60) 的反应，而在溶液中形成了一些其他产物，并对其为何发生给出了解释。这种一致性支持了基于与酮类和有机汞化合物相关反应结果的假设：富勒烯与电离室中其他化合物之间由 EI 引发的均裂反应结果可以预测富勒烯在溶液中对它们的反应活性。
