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

Abstract

<p>Terminal Ru(<small>V</small>)–imido species are thought to be as reactive to group transfer reactions as their Ru(<small>V</small>)–oxo homologues, but are less studied. With the electron-rich corrole ligand, relatively stable and isolable Ru(<small>V</small>)–arylimido complexes [Ru(<small>^<em>t</em></small>Bu–Cor)(NAr)] (H<small>₃</small>(<small>^<em>t</em></small>Bu–Cor) = 5,15-diphenyl-10-(<em>p-tert</em>-butylphenyl)corrole, Ar = 2,4,6-Me<small>₃</small>C<small>₆</small>H<small>₂</small> (Mes), 2,6-(<small>^<em>i</em></small>Pr)<small>₂</small>C<small>₆</small>H<small>₃</small> (Dipp), 2,4,6-(<small>^<em>i</em></small>Pr)<small>₃</small>C<small>₆</small>H<small>₂</small> (Tipp), and 3,5-(CF<small>₃</small>)<small>₂</small>C<small>₆</small>H<small>₃</small> (BTF)) can be prepared from [Ru(<small>^<em>t</em></small>Bu–Cor)]<small>₂</small> under strongly reducing conditions. This type of Ru(<small>V</small>)–monoarylimido corrole complex with <em>S</em> = 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(<small>^<em>t</em></small>Bu–Cor)(NAr)] (Ar = Mes, BTF) could undergo aziridination of styrenes and amination of benzylic C(sp<small>³</small>)–H bonds with up to 90% product yields.<br></p>