HCB11(CF3)(n)F(11-n)-: inert anions with high anodic oxidation potentials.
HCB11(CF3)(n)F(11-n)-: inert anions with high anodic oxidation potentials.
复制标题
HCB11(CF3)(n)F(11-n)-：具有高阳极氧化电位的惰性阴离子。
DOI：
10.1021/ja111035k
复制
发表时间：
2011
影响因子：
15
通讯作者：
J. Michl
中科院分区：
文献类型：
--
作者：
Matthew G. Fete;Z. Havlas;J. Michl
Cs salts of four of the title anions were prepared by fluorination of salts of partly methylated (n = 11, 10) or partly methylated and partly iodinated (n = 6, 5) CB(11)H(12)(-) anions. The CH vertex is acidic, and in the unhindered anion with n = 6 it has been alkylated. Neat Cs(+)[1-H-CB(11)(CF(3))(11)](-) is as treacherously explosive as Cs(+)[CB(11)(CF(3))(12)](-), but no explosions occurred with the salts of the other three anions. BL3YP/6-31G* gas-phase electron detachment energies of the title anions are remarkably high, 5-8 eV. Treated with NiF(3)(+) in anhydrous liquid HF at -60 °C, anions with n = 11 or 10 resist oxidation, whereas anions with n = 6 or 5 are converted to colored EPR-active species, presumably the neutral radicals [HCB(11)(CF(3))(n)F(11-n)](•). These are stable for hours at -60 °C after extraction into cold perfluorohexane or perfluorotri-n-butylamine solutions. On warming to -20 °C in a Teflon or quartz tube, the color and EPR activity disappear, and the original anions are recovered nearly quantitatively, suggesting that the radicals oxidize the solvent.
