Reactions of [Ir(COD)(PMe3)3]Cl with heteroaromatic compounds: Formation of an iridathiacycle, an iridaselenacycle and iridaazathiacycles

Reactions between [Ir(COD)(PMe3)3]Cl, 1, and the heteroaromatic compounds thiophene, selenophene and thiazole (and substituted thiazoles) are reported. Compound 1 acts as a convenient source of the very electron-rich “Ir(PMe3)3Cl” which is very active for oxidative addition reactions. All of the heteroaromatic compounds mentioned add via C–S or C–Se oxidative addition resulting in the insertion of the iridium forming 6-membered thia- or selena-iridacycles.Figure optionsDownload full-size imageDownload as PowerPoint slide

Graphical abstractThree types of iridium-containing heterocyclic rings are described in this paper. They are created via the insertion of an electron-rich iridium(I) species, “Ir(PMe3)3Cl”, into the C–S bond of thiophene and thiazoles as well as the C–Se bond of selenophene. These new heterocyclic systems are completely characterized including single-crystal X-ray diffraction.Figure optionsDownload full-size imageDownload as PowerPoint slideHighlights► [Ir(COD)(PMe3)3]Cl acts as a convenient source of the electron-rich “Ir(PMe3)3Cl”. ► [Ir(COD)(PMe3)3]Cl reacts with thiophene, and thiazoles to insert Ir into C–S bond. ► [Ir(COD)(PMe3)3]Cl reacts with selenophene to insert Ir into C–Se bond. ► Iridathiacycles, iridaselenacycles and iridaazathiacycles are all fully characterized. ► Ir, N, S ring system characterized by significant nitrogen basicity.