Electrospray ionization was employed to study the mass spectrometric behavior of the maleonitrile tetrathiacrown ethers mn12S4 (1) and mn13S4 (2) and maleonitrile pentathiacrown ether mn15S5 (3) and of their complexes with various metal salts (MX2, M = Pd, Pt, Ni, Co, Fe; X = Cl, CrCl3, Ni(BF4)2, TlPF6 or Cd(NO3)2) and Cu(SO3CF3)2. Both singly charged, [MXL]+ and [MXL2]+, and doubly charged complexes, [MLn]2+ (n = 2–5), were observed. The formation of the different complexes consisting of the transition metal ion, the counterion and the various crown ethers and their subsequent dissociation was also studied by collision-induced dissociation measurements which were also used to evaluate the relative stabilities of the complexes. It was found that the collisional voltages for the dissociation of the complexes were generally greater in the [MXL]+ complexes than in the corresponding [MXL2]+ complexes. Copyright © 2006 John Wiley & Sons, Ltd.