A variety of linear trisulfides were synthesized to assess the influence of the steric bulk and functional group compatibility on S-S metathesis in DMF (S124-S160). In general, rapid S-S metathesis was observed in 1 or 10 equivalents of DMF for a variety of combinations of alkyl, allyl, and benzyl trisulfides (Fig. ), as determined by GC-MS or 1 H NMR spectroscopy (S161-S185). Equilibrium was generally established within 1 hour at room temperature when 10 equivalents of DMF was used and no disulfides or tetrasulfides were ever observed, even after 24 hours of reaction. No metathesis was observed in the neat control reactions in which no DMF was added to the two liquid trisulfides. Slightly slower reaction rates were observed for larger alkyl groups (iPr and iBu) when only 1 equivalent of DMF was used. For trisulfides containing 1 or 2 very large groups such as tert-butyl or adamantyl groups, no S-S metathesis was observed at room temperature due to steric hindrance (Figure ). However, the metathesis of BnS3 t Bu and MeS3Me could be promoted in DMF at 100 ºC, while the there was no reaction at the same temperature when no solvent was used (Figure ). Interestingly, the diol in Figure was unreactive in the S-S metathesis in DMF, but its corresponding trimethylsilyl (TMS) ether underwent rapid S-S metathesis. This result highlights the sensitivity of the reaction to OH groups which may attenuate the reactivity of the trisulfide or an intermediate species (see below). Finally, the ability to manipulate the equilibrium composition of the reversible S-S metathesis reaction was demonstrated (Figure ). When an excess of dimethyl trisulfide (50 equivalents) and DMF were added to dibenzyl trisulfide, S-S metathesis provided the unsymmetric product (BnS3Me). This product could be isolated in 92% yield after extraction into pentane and distillation of the excess dimethyl trisulfide, demonstrating the preparative potential of this reaction in synthesis. As a further demonstration of the reversibility of the S-S metathesis reaction, BnS3Me was re-subjected to DMF and observed to undergo spontaneous S-S metathesis within minutes, generating a mixture of BnS3Me, BnS3Bn, and MeS3Me (Figure ).