A novel dimeric rhenium(IV) complex, [Re-2(SCH2CH2S)(4)], and a monomeric methyloxorhenium(V) complex, [CH3ReO(SCH2CH2S)PPh3], were synthesized from methyloxorhenium(V) complexes and characterized crystallographically. The structure of [Re-2(SCH2CH2S)(4)], the formation reaction of which showed surprising demethylation conceivably through the homolytic cleaveage of the rhenium-carbon bond, features distorted trigonal prismatic coordination of sulfurs around the metal center and a rhenium-rhenium triple bond. A revised structure, [Tc-2(SCH2CH2S)(4)], is proposed for a related technetium complex, originally identified as [Tc-2(SCR2CH2S)(2)(SCH=CHS)(2)] (Tisato et al. Inorg. Chem. 1993, 32, 2042). Additionally, a new compound, CH3Re(O)(SPh)(2)PPh3, was prepared.