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.
Improvement of resource efficiency of the catalytic isomerization process by mathematical modeling
