The three-component reaction of ReS4- (1), H2S, and unsaturated substrates (un = alkene, alkyne) affords the Re-V derivatives Re(S)(S(2)un)(SH)(2)(-). These adducts arise via the addition of H2S to intermediate dithiolates ReS2(S2C2R4)(-) and dithiolenes ReS2(S2C2R2)(-) The species (ReS[S2C2(tms)(2)](SH)(2))(-), [ReS(S2C7H10)(SH)(2)](-) (3), and [ReS(S2C2H4)(SH)(2)](-) are prepared according to this route. Similarly, the selenolate-thiolate complex [Res(S2C7H10)(SeH)(SH)](-) (5) is produced by the reaction of [ReS2(S2C7H10)](-) with H2Se. The corresponding reactions using benzenethiol in place of H2S afford the more thermally robust adducts {ReS[S2C2(tms)(2)](SH)(SPh)}(-), [Res(S2C7H10)(SH)(SPh)](-) (7), and [ReS(S2C2H4)(SH)(SPh)](-). Norbomanedithiolato compounds 3, 5, and 7 are obtained as pairs of isomers that differ in terms of the relative orientation of the norbornane bridgehead relative to the Re=S unit. The reaction of [ReS(S2C7H10)(SD)(2)](-) (3-d(2)) with H2S to give 3 is proposed to proceed via elimination of D2S and subsequent addition of H2S. Variable-temperature H-1 NMR measurements on the equilibrium of [ReS(S2C6H12)(SPh)(SH)](-) with 1, 1-hexene, and PhSH gave the following results: DeltaH = -7 (+/-1) kJ(.)mol(-1); DeltaS = 23 (+/-4) J(.)mol(-1.)K(-1). Solutions of ethanedithiol and 1 react with C-2(tms)(2) and C2H4 to give {ReS[S2C2(tms)(2)](S2C2H4)}(-) and [ReS(S2C2H4)(2)](-), respectively, concomitant with loss of H2S. The pathway for the ethanedithiol reaction is examined using 2-mercaptoethanol, affording {ReS[S2C2(tms)(2)](SC2H4OH)}(-), which does not cyclize. Treatment of a solution of diphenylbutadiyne and 1 with PhSH gives two isomers of the dithiolene (ReS(SH)(SPh)[S2C2Ph(C2Ph)])(-). The corresponding reaction of ethanedithiol, diphenylbutadiyne, and 1 affords the 1,4-diphenylbutadiene-1,2,3,4-tetrathiolate complex {[ReS(S2C2H4)](2)(S4C4Ph2)}(2-).