A spectroscopic investigation of complexes used to catalyze the oxidative carbonylation of toluene to p-toluic acid was conducted. Rhodium complexes were analyzed by 103Rh and 13C NMR, UV-visible spectroscopy, and infrared spectroscopy. In the presence of vanadium and oxygen, the resting state of the Rh-catalyst was found to exist as a Rh(III) complex with carbonyl and trifluoroacetate ligands, consistent with the structure Rh(CO)2(TFA)3. The 13C NMR spectrum of Rh(13CO)2(TFA)3 complex exhibited a carbonyl peak with an unusual degree of shielding, which resulted in the appearance of the carbonyl peak at an unprecedented upfield position in the 13C NMR spectrum. This shielding was caused by interaction of the carbonyl group with the trifluoroacetate ligand. In the absence of oxygen, the Rh(III) complex reduced to Rh(I), and the reduced form exhibited properties resembling the catalyst precursor. Structures and spectroscopic properties calculated using density functional theory agreed closely with the experimental results. The vanadium co-catalyst used to reoxidize Rh(I) to Rh(III) was similarly characterized by 51V NMR and UV-visible spectroscopy. The oxidized species corresponded to [(VO2)(TFA)]2, whereas the reduced species corresponded to (VO)(TFA)2. The spectroscopic results obtained in this study confirm the identity of the species that have been proposed to be involved in the Rh-catalyzed oxidative carbonylation of toluene to toluic acid.
