Efficient, new and direct synthetic routes for the syntheses of chromium complexes of some N,N-donors, based on the reactions of a chromium(III) chloride salt and silver(I) complexes of the corresponding ligands, have been described. It has been shown that syntheses of mixed-ligand complexes of desired compositions may easily be achieved by following these trans-metalation reaction routes. Comparison of the synthetic methodology with the reported methods has been noted.