Synthesis, Interconversion, and Structural Characterization of the Closo and Nido Clusters [(p-Cymene)3M3S2]2+and [(p-Cymene)3M3S2]0(M = Ru, Os)

John R. Lockemeyer, Thomas B. Rauchfuss, Arnold L. Rheingold

Research output: Contribution to journalArticle

Abstract

The first (arene)metal sulfido clusters are described. Salts of the dicationic clusters of the general formula [(p-cymene)3M3S2]2+ were prepared from the reaction of [(p-cymene)MCl2]2 (M = Ru, [1]2+; M = Os, [2]2+) with (Me3Si)2S, methanolic NaSH, or aqueous Na2S as sulfide sources. [1](PF6)2 cyrstallizes in the triclinic space group P1 with a = 10.495 (3) Å, b = 11.064 (3) Å, c = 18.230 (6) Å, α = 100.62 (2)°, β = 90.93 (3)°, γ = 115.40 (2)°, Z = 2, and dcalcd = 1.883 g cm-3. The dication [1]2+ exists as a closo trigonal-bipyramidal cluster with Ru-Ru distances of 2.763 (3)-2.796 (1) Å and an average Ru-S distance of 2.338 (2) Å. Cyclic voltammetric studies show that [1]2+ undergoes two one-electron reductions separated by only 0.137 V vs Ag/AgCl, and [2]2+ undergoes a simultaneous two-electron reduction at -0.761 V vs Ag/AgCl. Cobaltocene reduction of [1](PF6)2 gives dark blue [1]0. This neutral Ru3S2 cluster crystallizes in the triclinic space group P1 with a = 9.958 (3) Å, b = 10.270 (3) Å, c = 15.338 (5) Å, α = 78.26 (2)°, β = 85.92 (3)°, γ = 78.53 (2)°, Z = 2, and dcalcd = 1.700 g cm-3. [1]0 adopts a nido framework with two bonding Ru-Ru distances of 2.733 (1) and 2.712 (1) Å and a nonbonding Ru-Ru distance of 3.612 (1) Å. The average Ru-S distances are elongated with respect to the closo cluster. The cymene ligands are bound in an η6-fashion and are closer to the metal centers by an average of 0.015 (6) Å. The reduced cluster is highly reactive, and it is oxidized by H+ to regenerate the dicationic closo cluster.

Original languageEnglish (US)
Pages (from-to)5733-5738
Number of pages6
JournalJournal of the American Chemical Society
Volume111
Issue number15
DOIs
StatePublished - Jul 1 1989

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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