Electron-rich CpIr(biphenyl-2,2′-diyl) complexes with π-accepting carbon donor ligands


Cp*Ir III and CpIr III complexes have attracted interest as catalysts for oxidative transformations, and highly oxidizing iridium species are postulated as key intermediates in both catalytic water and C-H bond oxidation. Strongly electron-donating ligand sets have been shown to stabilize Ir IV complexes. We describe the synthesis and reactivity of complexes containing the CpIr(biphenyl-2,2′-diyl) moiety stabilized by a series of strong donor carbon-based ligands. The oxidation chemistry of these complexes has been characterized electrochemically, and a singly oxidized Ir IV species has been observed by X-band EPR for the complex CpIr(biph)(p-CNCH 2SO 2C 6H 4CH 3). © 2012 American Chemical Society.

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