Decacarbonyldihydridotriosmium

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.

Decacarbonyldihydridotriosmium
Names
IUPAC names
Decacarbonyldihydridotriosmium,
Decacarbonyl-1κ3C,2κ3C,3κ4C-di-μ-hydrido-1:2κ2H;1:2κ2H-triangulo-triosmium(3 OsOs)
Identifiers
3D model (JSmol)
Properties
H2Os3(CO)10
Molar mass 852.81 g/mol
Appearance Deep purple-violet crystals
Density 3.48 g/cm3
Boiling point decomposes
no
Solubility in other solvents reacts with Chlorocarbons
Structure
triangular cluster
Hazards
Main hazards Toxic
Related compounds
Related compounds
Os3(CO)12
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references

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. It is prepared by purging a solution of Os3(CO)12 in octane (or other inert solvent of similar boiling point) with H2.[2]

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.[3]

References

  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. Kaesz, H. D.; Glavee, G. N.; Angelici, R. J. (1990). Decacarbonyldi-μ-Hydridotriosmium: Os3(μ-H)2(CO)10. Inorganic Syntheses. 28. pp. 238–39. doi:10.1002/9780470132593.ch60. ISBN 978-0-470-13259-3.
  3. R. Bruce Calvert; John R. Shapley (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". J. Am. Chem. Soc. 99 (15): 5225–5226. doi:10.1021/ja00457a077.
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