Universität zu Köln

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:	Creators Email ORCID ORCID Put Code Bertocco, Philipp UNSPECIFIED UNSPECIFIED UNSPECIFIED Bolli, Christoph UNSPECIFIED UNSPECIFIED UNSPECIFIED Derendorf, Janis UNSPECIFIED UNSPECIFIED UNSPECIFIED Jenne, Carsten UNSPECIFIED UNSPECIFIED UNSPECIFIED Klein, Axel UNSPECIFIED orcid.org/0000-0003-0093-9619 UNSPECIFIED Stirnat, Kathrin UNSPECIFIED UNSPECIFIED UNSPECIFIED
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:	Faculty of Mathematics and Natural Sciences
Divisions:	Faculty of Mathematics and Natural Sciences > Department of Chemistry > Institute of Inorganic Chemistry
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language RAY CRYSTAL-STRUCTURE; SUBSTITUTION SYMMETRY; CATIONS; ANIONS; OXIDATION; SALTS Multiple languages Chemistry, Multidisciplinary Multiple languages
Refereed:	Yes
URI:	http://kups.ub.uni-koeln.de/id/eprint/25707