Ruthenium(v) terminal arylimido corroles: isolation, spectroscopic characterization and reactivity

Terminal Ru(v)–imido species are thought to be as reactive to group transfer reactions as their Ru(v)–oxo homologues, but are less studied. With the electron-rich corrole ligand, relatively stable and isolable Ru(v)–arylimido complexes [Ru((t)Bu–Cor)(NAr)] (H(3)((t)Bu–Cor) = 5,15-diphenyl-10-(p-tert-butylphenyl)corrole, Ar = 2,4,6-Me(3)C(6)H(2) (Mes), 2,6-((i)Pr)(2)C(6)H(3) (Dipp), 2,4,6-((i)Pr)(3)C(6)H(2) (Tipp), and 3,5-(CF(3))(2)C(6)H(3) (BTF)) can be prepared from [Ru((t)Bu–Cor)](2) under strongly reducing conditions. This type of Ru(v)–monoarylimido corrole complex with S = ½ was characterized by high-resolution ESI mass spectrometry, X-band EPR, resonance Raman spectroscopy, magnetic susceptibility, and elemental analysis, together with computational studies. Under heating/light irradiation (xenon lamp) conditions, the complexes [Ru((t)Bu–Cor)(NAr)] (Ar = Mes, BTF) could undergo aziridination of styrenes and amination of benzylic C(sp(3))–H bonds with up to 90% product yields.