Dualizing means applying the functor
$\mathrm{Hom}(\bullet,R)$. This is left exact but not right exact. So while $N \to M$ is surjective $\mathrm{Hom}(N,R) \to \mathrm{Hom}(M,R)$ is not necessarily. The $\mathrm{Ext}$ functor is the right derived functor of the $\mathrm{Hom}$ functor.
Dualizing means applying the functor $\mathrm{Hom}(\bullet,R)$. This is left exact but not right exact. So while $N \to M$ is surjective $\mathrm{Hom}(N,R) \to \mathrm{Hom}(M,R)$ is not necessarily. The $\mathrm{Ext}$ functor is the right derived functor of the $\mathrm{Hom}$ functor.