REACTIONS OF 29 TRANSITION-METAL CATIONS, IN THE SAME OXIDATION-STATEAND UNDER THE SAME GAS-PHASE CONDITIONS, WITH SULFUR

A total of 29 transition metals (all except Tc), all as ions M(+), hav e been reacted with gaseous S-8. The reactivities and reaction product s provide a unique set of comparative data on a fundamental reaction o f the elements. The results underlie the interpretation of many other processes and compounds in condensed phases. Series of product ions [M S(y)](+) are formed, with y generally starting at 4, and increasing wi th time through 8 up to 10, 12, 16, or 21 (for La+). A general mechani sm is proposed, in which the first {MS(8)}(+) encounter complex is rea ctive and undergoes S-S bond scission and rearrangement around the met al, such that [MS(8)](+) is not an early product. The early transition metals react faster than later members of the series, and third row m etals 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 [HgSy](+) (except for a very low yield of [HgS3](+)) and is remarkably less reactive with sulfur t han 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 someti mes observed and is believed to be formed by electron transfer from S- 8 to some [MS(y)](+) complexes. Interpretation of the rates of reactio n of the ions of groups 3, 4, and 5 with S-8 is complicated because th ey react with adventitious water in the cell forming ore-species. The results are discussed in the context of condensed-phase metal polysulf ide chemistry.