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

Ka-Pan Shing; Lin Qin; Liang-Liang Wu; Jie-Sheng Huang; Chi-Ming Che

doi:10.1039/d3sc02266h

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

Chem Sci. 2023 Sep 2;14(38):10602-10609. doi: 10.1039/d3sc02266h. eCollection 2023 Oct 4.

Authors

Ka-Pan Shing¹, Lin Qin¹, Liang-Liang Wu¹, Jie-Sheng Huang¹, Chi-Ming Che^{1

2}

Affiliations

¹ State Key Laboratory of Synthetic Chemistry, Department of Chemistry, The University of Hong Kong Pokfulam Road Hong Kong China cmche@hku.hk.
² HKU Shenzhen Institute of Research and Innovation Shenzhen China.

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.