Abstract
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(tBu-Cor)(NAr)] (H3(tBu-Cor) = 5,15-diphenyl-10-(p-tert-butylphenyl)corrole, Ar = 2,4,6-Me3C6H2 (Mes), 2,6-(iPr)2C6H3 (Dipp), 2,4,6-(iPr)3C6H2 (Tipp), and 3,5-(CF3)2C6H3 (BTF)) can be prepared from [Ru(tBu-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(tBu-Cor)(NAr)] (Ar = Mes, BTF) could undergo aziridination of styrenes and amination of benzylic C(sp3)-H bonds with up to 90% product yields.
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