Directed Design of a AuI Complex with a Reduced Mesoionic Carbene Radical‐Ligand: Insights from 1,2,3‐Triazolylidene Selenium Adducts and Extensive Electrochemical Investigations

BEERHUES, JULIA; NEUBRAND, MAREN; SOBOTTKA, SEBASTIAN; NEUMAN, NICOLÁS I.; ABERHAN, HANNES; CHANDRA, SHUBHADEEP; SARKAR, BIPRAJIT

CHEMISTRY-A EUROPEAN JOURNAL

WILEY-V C H VERLAG GMBH

Año: 2021

0947-6539

Carbene‐based radicals are important for both fundamental and applied chemical research. We herein report extensive electrochemical investigations of nine different 1,2,3‐triazolylidene selenium adducts. We found that the half‐wave potentials of the first reduction of the selones correlate with their calculated LUMO energies and LUMO energies of the corresponding triazolylidene based mesoionic carbenes (MICs). Furthermore, unexpected quasi‐reversiblility of the reduction of two triazoline selones, exhibiting comparable reduction potentials, was discovered. Through UV‐vis‐NIR‐ and EPR‐ spectroelectrochemical investigations supported by DFT calculations, the radical anion was unambiguously assigned to be triazoline centered. This electrochemical behavior was transferred to a triazolylidene‐type gold‐MIC phenyl complex resulting in a MIC‐radical coordinated AuI species. Apart from UV‐vis‐NIR‐ and EPR spectroelectrochemical investigations of the reduction, the reduced gold coordinated MIC‐radical complex was also formed in situ in the bulk through chemical reduction. This is the first report of a monodentate triazolylidene‐based MIC ligand that can be reduced to its anion radical in a metal complex. The results presented here provide design principles for stabilizing radicals based on MICs.