Reactions of 29 Transition Metal Cations, in the Same Oxidation State and under the Same Gas-Phase Conditions, with Sulfur

Abstract

A total of 29 transition metals (all except Tc), all as ions M(+), have been reacted with gaseous S(8). The reactivities and reaction products provide a unique set of comparative data on a fundamental reaction of the elements. The results underlie the interpretation of many other processes and compounds in condensed phases. Series of product ions [MS(y)()](+) are formed, with y generally starting at 4, and increasing with time through 8 up to 10, 12, 16, or 21 (for La(+)). A general mechanism is proposed, in which the first {MS(8)}(+) encounter complex is reactive and undergoes S-S bond scission and rearrangement around the metal, such that [MS(8)](+) is not an early product. The early transition metals react faster than later members of the series, and third row metals react about twice as fast as first row metals. The metals which are more chalcophilic in condensed-phase chemistry are apparently less so as M(+); Hg(+) does not form observable [HgS(y)()](+) (except for a very low yield of [HgS(3)](+)) and is remarkably less reactive with sulfur than most of the other metal ions. Simple electron transfer between M(+) and S(8) does not occur except possibly for Ir(+), but S(8)(+) is sometimes observed and is believed to be formed by electron transfer from S(8) to some [MS(y)()](+) complexes. Interpretation of the rates of reaction of the ions of groups 3, 4, and 5 with S(8) is complicated because they react with adventitious water in the cell forming oxo-species. The results are discussed in the context of condensed-phase metal polysulfide chemistry.

Study of Reactions of Silver and Sulfur Clusters

“…Thus the clusters are produced by laser ablation of the two samples, forming ions, and the ions collide to react with each other. The experiments show that the reaction products obtained by LDAR are similar to that obtained by FTICR, 8,9 indicating that this new technique is very effective for study of the reactions between clusters. In this paper, we also present the study of the photodissociation of the reaction products.…”

“…The ring S 8 molecule has a structure similar to the skull structure with D 4d symmetry. Gas phase sulfur exists mainly in the forms of S 6 , S 7 , and S 8 In comparison, we can see that the reaction products and the reaction mechanism by LDAR are different from those by FTICR. The former is of the reactions between the emitted species (atoms, molecules, and clusters) generated by laser ablation.…”

“…It is obvious that Ag + is more abundant than Ag 2 + and Ag 3 + . So, we can suggest that the products [AgS n ] + (n ) 4,8,12,16) are produced mainly from reactions between Ag + and S n .…”

“…5,6 Molecular sulfur can be reduced to S 2 -by most metals in condensed phase chemistry, 7 although sulfur does not react with metal ions in solution. 8,9 However, the reactions in the condensed phase are influenced strongly by the environment; therefore, the reactions in the gas phase are preferred to better understand the chemical reaction mechanisms.…”

“…20 The reactions of all the transition metal ions, [M + ], with sulfur have been reported, 8 and the study with Ag + was highlighted. 9 The reaction between silver ion Ag + and S 8 16 ] + . The compositions of these products are totally different from that of condensed phase compounds or that of Ag/S clusters produced from a Ag/S mixed sample, 11 without composition of a Ag 2 S unit.…”