Cyclometalated mono- and dinuclear Ir(III) complexes with "click"-derived triazoles and mesoionic carbenes.

Orthometalation at Ir(III) centers is usually facile, and such orthometalated complexes often display intriguing electronic and catalytic properties. By using a central phenyl ring as C-H activation sites, we present here mono- and dinuclear Ir(III) complexes with "click"-derived 1,2,3-triazole and 1,2,3-triazol-5-ylidene ligands, in which the wingtip phenyl groups in the aforementioned ligands are additionally orthometalated and bind as carbanionic donors to the Ir(III) centers. Structural characterization of the complexes reveal a piano stool-type of coordination around the metal centers with the "click"-derived ligands bound either with C^N or C^C donor sets to the Ir(III) centers. Furthermore, whereas bond localization is observed within the 1,2,3-triazole ligands, a more delocalized situation is found in their 1,2,3-triazol-5-ylidene counterparts. All complexes were subjected to catalytic tests for the transfer hydrogenation of benzaldehyde and acetophenone. The dinuclear complexes turned out to be more active than their mononuclear counterparts. We present here the first examples of stable, isomer-pure, dinuclear cyclometalated Ir(III) complexes with poly-mesoionic-carbene ligands.