The rapid metathesis of trisulfides observed in DMF and related solvents could, in principle, involve intermediate thiols, thiolates or thiyl radicals. However, the key metathesis reaction reliably and selectively generated trisulfides only: no disulfides and no tetrasulfides were formed. This was a curious result, and an unlikely outcome if thiolates or thiyl radicals were intermediates. To test whether these species were involved in the reaction, thiols, thiolates and thiyl radicals were independently generated and reacted with a trisulfide (S88-S94 and Figure ). In the first case, 1propane thiol (0.1 equivalents) was reacted with di-n-propyl trisulfide. While the reaction was slow, di-n-propyl disulfide and di-n-propyl tetrasulfide were detected in the first minute of reaction by GC-MS, with increasing formation over 24 hours. If 1-propane thiol was first deprotonated with sodium hydride to form the corresponding thiolate, reaction with di-n-propyl trisulfide in DMF led to rapid formation of a mixture of di-, tri-, and tetrasulfides (Figure ). Because the trisulfide metathesis in DMF provides only trisulfides, it is therefore unlikely to involve thiol and thiolate intermediates.