Decacarbonyldihydridotriosmium

Decacarbonyldihydridotriosmium
Names

IUPAC names Decacarbonyldihydridotriosmium, Decacarbonyl-1κ³C,2κ³C,3κ⁴C-di-μ-hydrido-1:2κ²H;1:2κ²H-triangulo-triosmium(3 Os—Os)
Identifiers
CAS Number	41766-80-7^Y
3D model (JSmol)	Interactive image
PubChem CID	139143320
InChI InChI=1S/10CO.3Os.2H/c101-2;;;;;/q;;;;;;;;;;;2+1;2*-1 Key: ABHQEXNWCLZGFV-UHFFFAOYSA-N
SMILES [H-].[H-].[C-]#[O+].[C-]#[O+].[C-]#[O+].[C-]#[O+].[C-]#[O+].[C-]#[O+].[C-]#[O+].[C-]#[O+].[C-]#[O+].[C-]#[O+].[Os].[Os+].[Os+]
Properties
Chemical formula	H₂Os₃(CO)₁₀
Molar mass	852.81 g/mol
Appearance	Deep purple-violet crystals
Density	3.48 g/cm3
Boiling point	decomposes
Solubility in water	insoluble
Solubility in other solvents	reacts with Chlorocarbons
Structure
Coordination geometry	triangular cluster
Hazards
Occupational safety and health (OHS/OSH):
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). Y verify (what is ^YN ?) Infobox references

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.

Structure and synthesis

The trinuclear cluster features an isosceles triangular array of metals with one short edge (r_Os-Os = 2.68 Å), which is spanned by the two hydride ligands, and two longer edges (r_Os-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

^ 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.
^ 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.
^ Kaesz, H. D. (1990). "Decacarbonyldi-μ-Hydridotriosmium: Os₃(μ-H)₂(CO)₁₀". Inorganic Syntheses. 28: 238–39. doi:10.1002/9780470132593.ch60.
^ 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.
^ 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.