Decacarbonyldihydridotriosmium

Decacarbonyldihydridotriosmium

Decacarbonyldihydridotriosmium

Chemical compound

Decacarbonyldihydridotriosmium is an organoosmium compound with the formula H2Os3(CO)10. This purple-violet crystalline air-stable cluster is noteworthy because it is electron-deficient and hence adds a variety of substrates.

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Structure and synthesis

The trinuclear cluster features an isosceles triangular array of metals with one short edge (rOs-Os = 2.68 Å), which is spanned by the two hydride ligands, and two longer edges (rOs-Os = 2.81 Å).[1] It can be described as Os(CO)4[Os(CO)3(μ-H)]2. The bonding in the Os2H2 subunit has been compared to the 3-center, 2e bonding in diborane. The molecule forms a variety of adducts with loss of H2.[2]

It is prepared by purging a solution of Os3(CO)12 in octane (or other inert solvent of similar boiling point) with H2.[3]

Os3(CO)12 + H2 → Os3H2(CO)10 + 2 CO

Reactions

The cluster reacts with a wide range of reagents under mild conditions. Illustrative is its reaction with diazomethane to give Os3(CO)10(μ-H)(μ-CH3), exhibiting an agostic interaction, the first identified in a metal cluster.[4][5]

References

  1. [1]
    Melvyn Rowen Churchill; Frederick J. Hollander; John P. Hutchinson (1977). "Structural studies on polynuclear osmium carbonyl hydrides. 5.Crystal structure and molecular geometry of di-μ-hydrido-decacarbonyltriosmium, (μ-H)2Os3(CO)10". Inorg. Chem. 28 (11): 2697–2700. doi:10.1021/ic50177a006.
  2. [2]
    Keister, J. B.; Shapley, J. R. "Solution Structures and Dynamics of complexes of Decacarbonyldihydrotriosmium with Lewis Bases" Inorganic Chemistry 1982, volume 21, pages 3304–3310; doi:10.1021/ic00139a011.
  3. [3]
    Kaesz, H. D. (1990). "Decacarbonyldi-μ-Hydridotriosmium: Os3(μ-H)2(CO)10". Inorganic Syntheses. 28: 238–39. doi:10.1002/9780470132593.ch60.
  4. [4]
    Calvert, R. Bruce; Shapley, John R. (1977). "Activation of Hydrocarbons by Unsaturated metal Cluster Complexes. 6. Synthesis and Characterization of Methyldecacarbonylhydridotriosmium, Methylenedecacarbonyldihydridotriosmium, and Methylidynenonacarbonyltrihydridotriosmium. Interconversion of Cluster-Bound Methyl and Methylene Ligands". Journal of the American Chemical Society. 99 (15): 5225–5226. doi:10.1021/ja00457a077.
  5. [5]
    Calvert, R. Bruce; Shapley, John R. (1978). "Decacarbonyl(methyl)hydrotriosmium: NMR Evidence for a Carbon...Hydrogen...Osmium Interaction". Journal of the American Chemical Society. 100 (24): 7726–7727. doi:10.1021/ja00492a047.
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