Electrospray mass spectrometric studies of the complexational behavior of maleonitrile thiacrown ethers with various metals

Electrospray ionization was employed to study the mass spectrometric behavior of the maleonitrile tetrathiacrown ethers mn12S 4 (1) and mn13S 4 (2) and maleonitrile pentathiacrown ether mn15S 5 (3) and of their complexes with various metal salts (MX 2 , M = Pd, Pt, Ni, Co, Fe; X = Cl, CrCl 3 , Ni(BF 4 ) 2 , TlPF 6 or Cd(NO 3 ) 2 ) and Cu(SO 3 CF 3 ) 2 . Both singly charged, [MXL] + and [MXL 2 ] + , and doubly charged complexes, [ML n ] 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 [MXL 2 ] + complexes. Copyright © 2006 John Wiley & Sons, Ltd.