Details

Autor(en) / Beteiligte

• Rokob, Tibor András
• Rulíšek, Lubomír
• Šrogl, Jiří
• Révész, Ágnes
• Zins, Emilie L
• Schröder, Detlef

Titel

On the Mechanism of the Copper-Mediated C–S Bond Formation in the Intramolecular Disproportionation of Imine Disulfides

Ist Teil von

• Inorganic chemistry, 2011-10, Vol.50 (20), p.9968-9979

Ort / Verlag

United States: American Chemical Society

Erscheinungsjahr

2011

Link zum Volltext

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• The mechanism of the copper-mediated disproportionation of aromatic imine disulfides to benzothiazoles in the gas phase is investigated by experimental and theoretical methods. Application of infrared multiphoton dissociation and hydrogen/deuterium exchange experiments combined with density functional theory (DFT) calculations of the relevant molecular structures and the associated infrared spectra allows the identification of the observed ionic intermediates. The theoretical investigation of the possible reaction pathways supported by collision-induced dissociation experiments provides a consistent mechanistic picture of the reaction catalyzed by a single copper(I) ion. Activation of the substrate proceeds via homolytic sulfur–sulfur bond cleavage, yielding metal complexes in the formal +3 oxidation state; carbon–sulfur coupling and hydrogen-atom transfer complete the transformation to the products. Exploratory studies demonstrate that in the gas phase, the disproportionation of the imine disulfide can also be mediated by other metal ions via different either homo- or heterolytic mechanisms without involving high-valent intermediates.