Arene C–H activation using Rh(i) catalysts supported by bidentate nitrogen chelates

Abstract

The Rh(I) complexes [(^FlDAB)Rh(coe)(TFA)] (1) and [(BOZO)Rh(coe)(TFA)] (2) [^FlDAB = N,N-bis-(pentafluorophenyl)-2,3-dimethyl-1,4-diaza-1,3-butadiene, coe = cyclooctene, TFA = trifluoroacetate, BOZO = bis(2-oxazolin-2-yl)] are efficient catalyst precursors for H/D exchange between arenes and DTFA. Catalyst precursor 1 exhibits a TOF of 0.06 s⁻¹ at 150 °C for benzene H/D exchange. DFT calculations revealed that H/D exchange through reversible oxidative addition or internal electrophilic substitution of benzene is a viable pathway.