A naphthalene-based heterobimetallic triazolylidene IrIII/PdII complex: regioselective to regiospecific C–H activation, tandem catalysis and a copper-free Sonogashira reaction

Abstract

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.