Ag₂O versus Cu₂O in the Catalytic Isomerization of Coordinated Diaminocarbenes to Formamidines: A Theoretical Study

DFT theoretical calculations for the Ag₂O-induced isomerization process of diaminocarbenes to formamidines, coordinated to Mn(I), have been carried out. The reaction mechanism found involves metalation of an N-H residue of the carbene ligand by the catalyst Ag₂O and the formation of a key transition state showing a μ-η²:η² coordination of the formamidinyl ligand between manganese and silver, which allows a translocation process of Mn(I) and silver(I) ions between the carbene carbon atom and the nitrogen atom, before the formation of the formamidine ligand is completed. Calculations carried out using Cu₂O as a catalyst instead of Ag₂O show a similar reaction mechanism that is thermodynamically possible, but highly unfavorable kinetically and very unlikely to be observed, which fully agrees with experimental results.