Remarks on the process of homogeneous carbonylation of rhodium compounds by N,N-dimethylformamide

Reductive carbonylation of rhodium(III) chloride complexes, commercial RhCl3 · nH2O neutralized with BaCO3, (Me2NH2)2[RhCl5(DMF)], (PPh4)[RhCl4(H2O)2], RhCl3(DMF)3, RhCl3(CH3CN)3, RhCl3(CH3CN)2(DMF), [Rh(CO)2Cl3]2, and rhodium(I) complex, Rh(PPh3)3Cl, by N,N-dimethylformamide (DMF) is studied. The data obtained support the conception of direct carbonyl group transfer from DMF molecule to the Rh metal center. The mechanistic scheme of carbonylation process is refined and discussed with regard of new experimental results.