Experiments on the collisional activation of [Mn.(pyridine) n ] 2 + have revealed the presence of a new charge transfer channel, whereby clusters of the form (pyridine) k + for k=<3 are observed when n=<6. Several possible metal-ligand configurations are considered including sandwich and charged-separated structures. It is concluded that the complexes consist of a central doubly charged metal ion, and that electron transfer from a molecule is accompanied by the simultaneous association and removal of nearest neighbour ligands.