A. N. Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences, 28 Vavilov Str, 119991 GSP-1 Moscow V-334, Russia.
J Phys Chem A. 2009 Dec 10;113(49):13700-10. doi: 10.1021/jp906058q.
Interaction of C(60) with organo- and organoelement mercurials (CF(3)HgBr, PhHgBr, p-CH(3)C(6)H(4)HgBr, p-CH(3)OC(6)H(4)HgCl, CF(3)HgPh, Ph(2)Hg, (o-carborane-9-yl)(2)Hg, (m-carborane-9-yl)(2)Hg, (p-carborane-9-yl)(2)Hg, and (m-carborane-9-yl)HgCl) in the ionization chamber (IC) of the electron impact (EI) ion source of a mass spectrometer at 250-300 degrees C results in the transfer of the corresponding organic or organoelement radicals from the mercurials to the fullerene. Some of the processes are accompanied by hydrogen addition. C(70) reacts with Ph(2)Hg and (o-carborane-9-yl)(2)Hg at 300 degrees C in a similar fashion. A homolytic reaction path is considered for the reactions. It suggests both the thermal and EI initiated homolytic dissociation of the mercurials to the intermediate organic or organoelement radicals followed by their interaction with the fullerenes at the metallic walls of the IC. When EI is involved, the dissociation is supposed to occur via superexcited states (the excited states with the electronic excitation energies higher than the first ionization potentials) of the mercury reagents, with possible contribution of the process proceeding via their molecular ions. In line with the results obtained in the IC, C(60) reacts with Ph(2)Hg and (o-carborane-9-yl)(2)Hg under UV-irradiation in benzene and toluene solutions to furnish phenyl and carboranyl derivatives of the fullerene, respectively, some also containing the acquired hydrogen atoms. EPR monitoring of the processes has shown the formation of phenylfullerenyl and o-carborane-9-yl-fullerenyl radicals. g-Factors and hyperfine coupling (hfc) constants with (10)B, (11)B, and (13)C nuclei of both the latter and m-carborane-9-yl-fullerenyl radical formed in the reaction of C(60) with (m-carborane-9-yl)(2)Hg have been determined by the special EPR studies. The unusually great chemically induced dynamic electron polarization (CIDEP) of the latter radical where even the (13)C satellite lines are polarized has been observed and is discussed in terms of both radical-triplet-pair and radical-pair mechanisms. The similar CIDEP effect is also intrinsic to the o-carborane-9-yl-fullerenyl radical obtained under the same conditions. The analogous transfer of the carboranyl radicals from (o-carborane-9-yl)(2)Hg to C(60) occurs when their mixture is boiled in (t)BuPh for 10-15 h.
在电子冲击（EI）质谱仪离子源的电离室内，在 250-300°C 的温度下，C(60)与有机汞和有机汞化合物（CF(3)HgBr、PhHgBr、p-CH(3)C(6)H(4)HgBr、p-CH(3)OC(6)H(4)HgCl、CF(3)HgPh、Ph(2)Hg、(o-硼烷-9-基)(2)Hg、(m-硼烷-9-基)(2)Hg、(p-硼烷-9-基)(2)Hg 和 (m-硼烷-9-基)HgCl）相互作用，导致相应的有机或有机汞自由基从汞化合物转移到富勒烯上。其中一些过程伴随着氢的加成。在 300°C 下，C(70)以类似的方式与 Ph(2)Hg 和 (o-硼烷-9-基)(2)Hg 反应。该反应被认为是通过均裂反应途径进行的。它表明汞化合物在电离室内的金属壁上通过热和 EI 引发的均裂分解形成中间有机或有机汞自由基，然后与富勒烯相互作用。当涉及 EI 时，假设通过汞试剂的超激发态（电子激发能高于第一电离势的激发态）发生离解，可能的过程还涉及它们的分子离子。与在电离室内获得的结果一致，C(60)在苯和甲苯溶液中通过 UV 照射与 Ph(2)Hg 和 (o-硼烷-9-基)(2)Hg 反应，分别生成富勒烯的苯基和硼烷衍生物，其中一些还含有获得的氢原子。EPR 监测表明形成了苯基富勒烯基和 o-硼烷-9-基富勒烯基自由基。通过特殊的 EPR 研究确定了形成于 C(60)与 (m-硼烷-9-基)(2)Hg 反应中的后者和 m-硼烷-9-基富勒烯基自由基的 g 因子和与（10）B、（11）B 和（13）C 核的超精细耦合（hfc）常数。观察到了在相同条件下获得的 o-硼烷-9-基富勒烯基自由基中异常大的化学诱导动态电子极化（CIDEP），甚至极化了（13）C 卫星线，并根据自由基三重态对和自由基对机制进行了讨论。在相同条件下，当它们的混合物在（t）BuPh 中煮沸 10-15 小时时，类似的硼烷基自由基从（o-硼烷-9-基）（2）Hg 向 C(60)的转移也会发生。
