Cleavage of Metal-Metal Bonds in Heteronuclear Clusters. Reactions of Os33-S)(μ32-SCH2)(CO)8(PMe2Ph) with HCl and P(OMe)3

Richard D. Adams, Nancy M. Golembeski, John P. Selegue

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18 Scopus citations

Abstract

The reactions of the cluster Os33-S)(μ32-SCH2)(CO)8(PMe2Ph) (I), which contains a thioformaldehyde ligand, with HCl and P(OMe)3 have been investigated. The reaction of I with HCl yields an addition product HOs33-S)(μ32-SCH2)(CO)8(PMe2Ph)Cl (II), which has been characterized by X-ray crystallographic methods: space group P21/c, at 23 °C; a = 10.423 (2) Å, b = 11.014 (5) Å, c = 22.743 (9) Å, β = 101.98 (3); V = 2554 (3) Å3; Z = 4; ρcalcd = 2.72 g/cm3. For 2689 reflections (Fo ≥ 3.0 σ(Fo2)) R1 = 0.044 and R2 = 0.048. The molecule contains a group of three osmium atoms but only one osmium-osmium bond. The third osmium is linked to the others by a triply bridging sulfide and triply bridging thioformaldehyde ligand. The addition of HCl to I results in cleavage of one of its osmium-osmium bonds. The reaction of I with P(OMe)3 yields the new molecule Os33-S)(μ32-SCH2)(CO)7(PMe2Ph)[P(OMe)3] (III). III was also analyzed by an X-ray crystallographic analysis: space group P1, at 23 °C; a = 10.694 (2) Å, b = 11.630 (3) Å, c = 12.675 (2) Å, α = 111.16 (2)°, β = 99.63 (2)°, γ = 92.36 (2)°; V = 1441 (1) Å3; Z = 2; ͡calcd = 2.55 g/cm3. For 4083 reflections (Fo ≥ 3.0σ(Fo2)) R1 = 0.035 and R2 = 0.038. III is formed from I by the substitution of one of the carbonyl ligands on the phosphine-substituted osmium atom with the P(OMe)3 ligand. Thus, as in I, III contains a cluster with two osmium-osmium bonds a triply bridging sulfide ligand and a triply bridging thioformaldehyde ligand. The nature of the formations of II and III is compared in terms of probable mechanisms.

Original languageEnglish
Pages (from-to)240-245
Number of pages6
JournalOrganometallics
Volume1
Issue number2
DOIs
StatePublished - 1982

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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