title: The Me3NB12Cl11.Radical: A Strong One-Electron Oxidizing Agent.
abstract: 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 [Me3NB12Cl11]-in liquid SO2revealed an oxidation wave at +2.59 V versus Fc0/+. The oxidation of Na[Me3NB12Cl11] with AsF5in liquid sulfur dioxide gives the boron-cluster-based radical Me3NB12Cl11.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 Me3NB12Cl11.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 [I5]+cation. These reactive cations are stabilized in the solid state by the weakly coordinating anion [Me3NB12Cl11]-, which was formed as a reduced product in the oxidation reactions.
authors.affiliation: Fakultät für Mathematik und Naturwissenschaften, Anorganische Chemie, Bergische Universität Wuppertal, Gaußstrasse 20, 42119, Wuppertal, Germany.
authors.forename: Philipp
authors.initials: P
authors.lastname: Bertocco
authors.affiliation: Fakultät für Mathematik und Naturwissenschaften, Anorganische Chemie, Bergische Universität Wuppertal, Gaußstrasse 20, 42119, Wuppertal, Germany.
authors.forename: Christoph
authors.initials: C
authors.lastname: Bolli
authors.affiliation: Fakultät für Mathematik und Naturwissenschaften, Anorganische Chemie, Bergische Universität Wuppertal, Gaußstrasse 20, 42119, Wuppertal, Germany.
authors.forename: Janis
authors.initials: J
authors.lastname: Derendorf
authors.affiliation: Fakultät für Mathematik und Naturwissenschaften, Anorganische Chemie, Bergische Universität Wuppertal, Gaußstrasse 20, 42119, Wuppertal, Germany. carsten.jenne@uni-wuppertal.de.
authors.forename: Carsten
authors.initials: C
authors.lastname: Jenne
authors.affiliation: EPR Spectroscopy,Institut für Anorganische Chemie, Department für Chemie, Universität zu Köln, Greinstrasse 6, 50939, Köln, Germany.
authors.forename: Axel
authors.initials: A
authors.lastname: Klein
authors.affiliation: EPR Spectroscopy,Institut für Anorganische Chemie, Department für Chemie, Universität zu Köln, Greinstrasse 6, 50939, Köln, Germany.
authors.forename: Kathrin
authors.initials: K
authors.lastname: Stirnat
keywords: boranes; halogenated dodecaborates; oxidation; radicals; weakly coordinating anions