Introducing a mixed-valent dirhodium(ii,iii) catalyst with increased stability in C–H amination

Abstract

A new mixed-valent Rh₂^II,III dimer, [Rh₂(espn)₂Cl] (espn²⁻ = α,α,α′,α′-tetramethyl-1,3-benzenedipropanamidate), is reported. This compound readily dissociates Cl⁻ at low concentrations in solution to form the active [Rh₂(espn)₂]⁺ catalyst, which performs intramolecular C–H amination with TONs > 1400. This work expands the scope of Rh₂^II,III dimers to nitrenoid chemistry.