Electron capture dissociation mass spectrometry of metallo-supramolecular complexes.

The electron capture dissociation (ECD) of metallo-supramolecular dinuclear triple-stranded helicate Fe(2)L(3)(4+) ions was determined by Fourier transform ion cyclotron resonance mass spectrometry. Initial electron capture by the di-iron(II) triple helicate ions produces dinuclear double-stranded complexes analogous to those seen in solution with the monocationic metal centers Cu(I) or Ag(I). The gas-phase fragmentation behavior [ECD, collision-induced dissociation (CID), and infrared multiphoton dissociation (IRMPD)] of the di-iron double-stranded complexes, (i.e., MS(3) of the ECD product) was compared with the ECD, CID, and IRMPD of the Cu(I) and Ag(I) complexes generated from solution. The results suggest that iron-bound dimers may be of the form Fe(I)(2)L(2)(2+) and that ECD by metallo-complexes allows access, in the gas phase, to oxidation states and coordination chemistry that cannot be accessed in solution.