Van der Waals clusters are weakly bound atomic/molecular systems and are an important medium for understanding micro-environmental chemical phenomena in bio-systems. The presence of neighboring atoms may open channels otherwise forbidden in isolated atoms/molecules. In hydrogen-bond clusters, proton transfer plays a crucial role, which involves mass and charge migration over large distances within the cluster and results in its fragmentation. Here we report an exotic transfer channel involving a heavy N + ion observed in a doubly charged cluster produced by 1 MeV Ne 8+ ions: (N 2 Ar) 2+ →N + +NAr +. The neighboring Ar atom decreases the N 2þ 2 barrier height and width, resulting in significant shorter lifetimes of the metastable molecular ion state N 2þ 2 (X 1 Σ þ g). Consequently, the breakup of the covalent N + −N + bond, the tunneling out of the N + ion from the N 2þ 2 potential well, as well as the formation of an N−Ar + bound system take place almost simultaneously, resulting in a Coulomb explosion of N + and NAr + ion pairs.