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.