Stoichiometric Oxy Functionalization and CH Activation Studies of Cyclometalated Iridium(III) 6-Phenyl-2,2‘-Bipyridine Hydrocarbyl Complexes

A well-defined, thermal-, air-, and protic-stable, bis-bidentate, cyclometalated Ir(III) complex, Ir(NC)(NNtBu)CH3OTf, (2-CH3; NC = κ2-6-phenyl-2,2‘-bipyridine, NNtBu = κ2-4,4‘-di-tert-butyl-2,2‘-bipyridine) has been shown to undergo oxy functionalization with oxidants such as PhI(X)2 (X = OAc, TFA) to generate CH3X (X = OAc, TFA, OTf) in yields ranging from 36 to 67% in CH2Cl2 at ambient temperatures. 2-CH3 is also competent for CH activation, undergoing stoichiometric CH activation in benzene, and catalyzes the H/D exchange reaction between benzene and acids (acetic and trifluoroacetic acid).