Ir(IV) Sulfoxide-Pincer Complexes by Three-Electron Oxidative Additions of Br2 and I2. Unprecedented Trap-Free Reductive Elimination of I2 from a formal d5 Metal

Oxidative addition of 1.5 equiv of bromine or iodine to a Ir(I) sulfoxide pincer complex affords the corresponding Ir(IV) tris-bromido or tris-iodido complexes, respectively. The unprecedented trap-free reductive elimination of iodine from the Ir(IV)-iodido complex is induced by coordination of ligands or donor solvents. In the case of added I-, the isostructural tris-iodo Ir(III)-ate complex is quickly generated, which then can be readily reoxidized to the Ir(IV)-iodido complex with FcPF(6) or electrochemically. DFT calculations indicate an inverted ligand field in the Ir(IV) complexes and favor dinuclear pathways for the reductive elimination of iodine from the formal d(5) metal center.

Automated summary

The oxidative addition of bromine or iodine to an Ir(I) sulfoxide pincer complex leads to the formation of Ir(IV) tris-bromido or tris-iodido complexes, respectively. The reductive elimination of iodine from the Ir(IV)-iodido complex can be achieved without any traps by coordinating ligands or donor solvents. The addition of I- results in the quick generation of an isostructural tris-iodo Ir(III)-ate complex, which can be easily reoxidized back to the Ir(IV)-iodido complex.