| Fourier transform ion cyclotron resonance (FTICR) mass spectrometry combined with laser desorbtion technique is applied to study several types of novel organometallic ions in the gas-phase.; The polyhydrido trimethylphosphine rhenium complex, ReH7(PMe 3)2, and fragment ions, ReHx(PMe3) 2+/–, were generated and examined in the mass spectrometer to determine their structures or characters. The ion-molecule reaction results indicate that ReH7(PMe3)2 prefers to lose molecular hydrogens, to demerit and to be attached by the electron rich atom/molecule.; The σ-bond, Π-bond and M=S, M=O, M=CH2 bond ligand containing metal-ligand ions react with tert-butyl isocyanide to generate different products. The two kinds of imidoly ion/dipole complexes are formed as initial step for these reactions based on bond type and bond energy of the metal-ligand complex. Consequently, reaction mechanisms and product distributions depend on generated imidoly ion/dipole complexes.; The generation and characterization of transition-metal distonic ions, which contain the metal charge site spatially separated from the radical site are reported. The fluorine-substituted metal distonic ion IFe+C 6F4• was formed by rearrangement of a conventional metal cation, Fe+C6F4I. The metal distonic ion structure of this ion was demonstrated by ion-molecule reactions and collision-induced dissociation. Fluorine substitution on the benzene ring facilitates iodine atom migration by the strong inductive withdrawal of electrons and forming the dπ-pπ bond. However, the non-fluorine-substituted metal ion, Fe+C6H4I does not rearrange to the metal distonic ion structure. Nascent metal distonic ions, Fe +C6F4• and Fe+C 6H4•, rearrange to linear diyne-ene structures through metal biradical para-benzyne as intermediates. The study of novel transition-metal distonic ions reveals a whole new area of organometallic ion chemistry. |
