Influence of H2S and thiols on the binding of alkenes and alkynes to ReS4-: The spectator sulfido effect

J. A. Dopke, S. R. Wilson, T. B. Rauchfuss

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The three-component reaction of ReS4- (1), H2S, and unsaturated substrates (un = alkene, alkyne) affords the Re(V) derivatives Re(S)(S2un)(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)]-. Norbornanedithiolato 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-d2) with H2S to give 3 is proposed to proceed via elimination of D2S and subsequent addition of H2S. Variable-temperature 1H NMR measurements on the equilibrium of [ReS(S2C6H12)(SPh)(SH)]- with 1, 1-hexene, and PhSH gave the following results: ΔH = -7 (±1) kJ·mol-1; ΔS = 23 (±4) J·mol-1·K-1. Solutions of ethanedithiol and 1 react with C2(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-.

Original languageEnglish (US)
Pages (from-to)5014-5021
Number of pages8
JournalInorganic Chemistry
Issue number22
StatePublished - Oct 30 2000

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry


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