Ligand-centered reactivity of a pseudo-dearomatized phosphorus-nitrogen PN3P∗ rhodium complex towards molecular oxygen at room temperature

Abstract

The ligand of an organometallic complex is typically considered as a spectator which can be modified to tune the steric and electronic properties of the coordination environment. We herein demonstarted a PN3P∗Rh-CO pincer system where one of the C-H bonds of the pseudo-dearomatized pyridine ring was oxidized by O2 at room temperature to create an α,β-unsaturated carbonyl functionality on the ligand backbone. The resulting metal complex with the post-modified PN3P ligand readily reacts with thiophenol and 4-methylaniline to afford the corresponding oxidative Michael addition products.