The use of lasers to produce gas phase ions from involatile systems has allowed us to use mass spectrometry to study monopositive ions of a majority of the elements in the periodic table. These pristine species have been reacted with sulfur molecules to give some interesting products. The resulting reactions are not always what might be predicted from known condensed phase chemistry. The major missing factors in gas phase chemistry are the solvent and crystal packing forces. The solvent effect on the stability and reactions of ions cannot be underestimated and examples will be given to highlight this effect. The insolubility of a compound in a solvent and the crystal structure formation can also have a profound effect on the apparent 'stable' products of reactions in the condensed phase. In the gas phase we can study the fundamental reactivities of ions without these extraneous forces. The reaction rates and pathways can lead us to a better understanding of how reactivity varies in a group such as the Group II elements or a series of elements such as the transition metals.

Anions can also be produced by laser ablation of metal compounds and using mass spectrometry we are able to identify molecular forms of non-molecular solids. Most metal sulfides are non-molecular solids insoluble in all solvents that do not specifically react to release sulfur or hydrogen sulfides. Laser ablation of some first row transition metal sulfides has yielded over 290 new molecular forms of metal sulfides as their anions. There are 80 new molecular forms of cobalt sulfide! Some of these cluster anions [M_xS_y] are similar to the metal sulfur cores of condensed phase cluster systems and their identification might lead to the discovery of as yet unknown metal sulfide cluster compounds.

Our mass spectrometric studies can identify ions, reveal their stability and reactivities but not tell us directly about structure. Even spectroscopic examination of the cluster ions with more than about five metals may give us only partial answers about structure. Thus we have used non-local density functional calculations to reveal the lowest energy structures for some of our ions. Some examples of these results will be reported.

The mass spectrometry has been carried out using FTICR where ions can be trapped for many tens of seconds. Laser ablation can produce ions from the most refractory materials and we have used a Nd-YAG laser mainly at the fundamental frequency. Density functional calculations have been carried out using the program DMol.