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Organometallics. 2012 Oct 20;31(20):7158-7164.

Electron-Rich CpIr(biphenyl-2,2'-diyl) Complexes with π-Accepting Carbon Donor Ligands.

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  • 1Department of Chemistry, Yale University, P.O. Box 208107, New Haven, Connecticut 06520-8107, United States.


Cp*IrIII and CpIrIII 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 IrIV 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 IrIV species has been observed by X-band EPR for the complex CpIr(biph)(p-CNCH2SO2C6H4CH3).

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