Reductive functionalization of a rhodium(III)-methyl bond by electronic modification of the supporting ligand

Net reductive elimination (RE) of MeX (X = halide or pseudo-halide: Cl(-), CF3CO2(-), HSO4(-), OH(-)) is an important step during Pt-catalyzed hydrocarbon functionalization. Developing Rh(I/III)-based catalysts for alkane functionalization is an attractive alternative to Pt-based systems, but very few examples of RE of alkyl halides and/or pseudo-halides from Rh(III) complexes have been reported. Here, we compare the influence of the ligand donor strength on the thermodynamic potentials for oxidative addition and reductive functionalization using [(t)Bu3terpy]RhCl (1) {(t)Bu3terpy = 4,4',4''-tri-tert-butylpyridine} and [(NO2)3terpy]RhCl (2) {(NO2)3terpy = 4,4',4''-trinitroterpyridine}. Complex 1 oxidatively adds MeX {X = I(-), Cl(-), CF3CO2(-) (TFA(-))} to afford [(t)Bu3terpy]RhMe(Cl)(X) {X = I(-) (3), Cl(-) (4), TFA(-) (5)}. By having three electron-withdrawing NO2 groups, complex 2 does not react with MeCl or MeTFA, but reacts with MeI to yield [(NO2)3terpy]RhMe(Cl)(I) (6). Heating 6 expels MeCl along with a small quantity of MeI. Repeating this experiment but with excess [Bu4N]Cl exclusively yields MeCl, while adding [Bu4N]TFA yields a mixture of MeTFA and MeCl. In contrast, 3 does not reductively eliminate MeX under similar conditions. DFT calculations successfully predict the reaction outcome by complexes 1 and 2. Calorimetric measurements of [(t)Bu3terpy]RhI (7) and [(t)Bu3terpy]RhMe(I)2 (8) were used to corroborate computational models. Finally, the mechanism of MeCl RE from 6 was investigated via DFT calculations, which supports a nucleophilic attack by either I(-) or Cl(-) on the Rh-CH3 bond of a five-coordinate Rh complex.