Effects of Li$^+$ and Ag$^+$ Ions on the Rotational Barrier in Acetamide and propionamide System

Effects of Li$^+$ and Ag$^+$ Ions on the Rotational Barrier in Acetamide and propionamide System

The influences of $LiNO_3\;and\;AgNO_3$ on the N-C(O) rotational barrier of N,N-dimethylacetamide and N,N-dimethylpropionamide have been investigated. The rotational activation free energy $({\Delta}G^{\neq})\;for\;Li^{+}$-amide complexes is found to increase with increasing salt concentration. On the other hand, that for $Ag^+$-amide complexes increases in the presence of $Ag^+$ ion up to 0.25 M ion concentration and then decreases as the concentration of $Ag^+$ ion is further increased. Such an unusual behavior of $Ag^+$-amide complexes has been interpreted in terms of ion-pairing and diluent effect on the amides. However, $^{13}C$ nmr chemical shift data for the amides have shown that both of these ions interact primarily with the carbonyl group in amides.