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

A new mixed-valent Rh2II{,}III dimer{,} [Rh2(espn)2Cl] (espn2- = [small alpha]{,}[small alpha]{,}[small alpha][prime or minute]{,}[small alpha][prime or minute]-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 Rh2II{,}III dimers to nitrenoid chemistry.

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