The coordination of metalloligands to derive modified properties of the metal functionality is one of the interesting strategies practiced in materials chemistry and catalysis. In this work, a pendant terpyridine ligand has been utilized for templating a Cp*IrIII(NHC)-based (NHC = N-heterocyclic carbene) oxidation precatalyst to assess its modified oxidative behavior via electrochemical, UV-vis spectroscopic, and catalytic probes. These studies suggested that the coordination-template enhances the electron-deficiency at the IrIII redox center and affects the nature of the oxidized high-valent Ir-oxo species during chemical oxidation. Moreover, both the premodified and postmodified Cp*IrIII(NHC)-based complexes were found to be equally efficient in catalytic sp3 C–H oxidation reactions with NaIO4 as a mild sacrificial oxidant.

The coordination of metalloligands to derive modified properties of the metal functionality is one of the interesting strategies practiced in materials chemistry and catalysis. In this work, a pendant terpyridine ligand has been utilized for templating a Cp*IrIII(NHC)-based (NHC = N-heterocyclic carbene) oxidation precatalyst to assess its modified oxidative behavior via electrochemical, UV-vis spectroscopic, and catalytic probes. These studies suggested that the coordination-template enhances the electron-deficiency at the IrIII redox center and affects the nature of the oxidized high-valent Ir-oxo species during chemical oxidation. Moreover, both the premodified and postmodified Cp*IrIII(NHC)-based complexes were found to be equally efficient in catalytic sp3 C–H oxidation reactions with NaIO4 as a mild sacrificial oxidant.