A naphthalene-based heterobimetallic triazolylidene Ir^III/Pd^II complex: regioselective to regiospecific C-H activation, tandem catalysis and a copper-free Sonogashira reaction

Heterobimetallic complexes featuring mesoionic carbene (MIC) donor ligands are gaining enormous popularity in tandem catalysis owing to the combined action of two different metal centers during catalysis. A rare version of the heterobimetallic Pd^II/Ir^III complex possessing a cyclometalated mesoionic carbene (MIC) ligand is presented along with the analogous homodinuclear Pd^II complex. A sterically controlled regiospecific cyclometalation towards the formation of a six-membered ring complex over a five-membered ring complex has been performed using a naphthalene-based bis-MIC ligand platform. The interplay between regioselective vs. regiospecific C-H bond activation for the synthesis of cyclometalated Ir^III complexes has also been demonstrated using the corresponding naphthyl-derived mono-imidazolylidene ligand. Both homodinuclear Pd^II and heterobimetallic Pd^II/Ir^III complexes have been characterized using standard spectroscopic techniques including ¹H, ¹³C{¹H}, 2D correlation NMR spectroscopy and ESI mass spectrometry. The structure of the cyclometalated heterobimetallic complex has been established by single crystal XRD. The heterobimetallic complex has been employed as a pre-catalyst in the tandem Suzuki-Miyaura/transfer hydrogenation reaction and the homobimetallic Pd^II complex has been successfully employed as a catalyst in both the Sonogashira coupling and α-arylation of 1-methyl-2-oxindole.