The influence of noncovalent interactions in structural arrangements has been recognized for many years. 1–8 More recently, their role in different chemical processes has been increasingly acknowledged. 9–13 As such, the potential of hydrogen or halogen bonding as the directing force for catalysis has been assessed in many organic transformations. 14–20 Surprisingly, polymerization processes are an important class of catalytic reactions where the effect of the noncovalent interactions has scarcely been evaluated. Most of the studies reported refer to ring-opening polymerization (ROP), Ziegler–Natta