Bertocco, Philipp, Bolli, Christoph, Derendorf, Janis, Jenne, Carsten, Klein, Axel ORCID: 0000-0003-0093-9619 and Stirnat, Kathrin (2016). The Me3NB12Cl11 center dot Radical: A Strong One-Electron Oxidizing Agent. Chem.-Eur. J., 22 (45). S. 16032 - 16037. WEINHEIM: WILEY-V C H VERLAG GMBH. ISSN 1521-3765

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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 SO2 revealed an oxidation wave at +2.59 V versus Fc(0/+). The oxidation of Na[Me3NB12Cl11] with AsF5 in liquid sulfur dioxide gives the boron-cluster-based radical Me3NB12Cl11 center dot 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 center dot 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 [Me3NB12Cl11](-), which was formed as a reduced product in the oxidation reactions.

Item Type: Journal Article
Creators:
CreatorsEmailORCIDORCID Put Code
Bertocco, PhilippUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Bolli, ChristophUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Derendorf, JanisUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Jenne, CarstenUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Klein, AxelUNSPECIFIEDorcid.org/0000-0003-0093-9619UNSPECIFIED
Stirnat, KathrinUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
URN: urn:nbn:de:hbz:38-257072
DOI: 10.1002/chem.201603924
Journal or Publication Title: Chem.-Eur. J.
Volume: 22
Number: 45
Page Range: S. 16032 - 16037
Date: 2016
Publisher: WILEY-V C H VERLAG GMBH
Place of Publication: WEINHEIM
ISSN: 1521-3765
Language: English
Faculty: Unspecified
Divisions: Unspecified
Subjects: no entry
Uncontrolled Keywords:
KeywordsLanguage
RAY CRYSTAL-STRUCTURE; SUBSTITUTION SYMMETRY; CATIONS; ANIONS; OXIDATION; SALTSMultiple languages
Chemistry, MultidisciplinaryMultiple languages
Refereed: Yes
URI: http://kups.ub.uni-koeln.de/id/eprint/25707

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