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The Me 3 NB 12 Cl 11 . Radical: A Strong One‐Electron Oxidizing Agent
Author(s) -
Bertocco Philipp,
Bolli Christoph,
Derendorf Janis,
Jenne Carsten,
Klein Axel,
Stirnat Kathrin
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201603924
Subject(s) - oxidizing agent , chemistry , inorganic chemistry , electron paramagnetic resonance , oxidation state , ion , spectroscopy , yield (engineering) , ionization , metal , materials science , organic chemistry , nuclear magnetic resonance , physics , quantum mechanics , metallurgy
Strong oxidizing agents often contain fluorine and are not compatible with substrates forming strong element–fluorine bonds. Therefore, there is need for new strong oxidizers. Cyclic voltammetric measurements on the weakly coordinating anion [Me 3 NB 12 Cl 11 ] − in liquid SO 2 revealed an oxidation wave at +2.59 V versus Fc 0/+ . The oxidation of Na[Me 3 NB 12 Cl 11 ] with AsF 5 in liquid sulfur dioxide gives the boron‐cluster‐based radical Me 3 NB 12 Cl 11 . as a dark blue solid in quantitative yield. The radical was characterized by vibrational, NMR, and EPR spectroscopy and by its crystal structure. To explore the potential of the radical Me 3 NB 12 Cl 11 . to act as a strong oxidizing agent, it was reacted with different compounds having high ionization energies. Thianthrene (ionization energy 7.8 eV) and hexabromobenzene (8.8 eV) were oxidized to the corresponding cations. The reaction with elemental iodine (9.3 eV) gave the [I 5 ] + cation. These reactive cations are stabilized in the solid state by the weakly coordinating anion [Me 3 NB 12 Cl 11 ] − , which was formed as a reduced product in the oxidation reactions.