Decacarbonyldihydridotriosmium

Last updated
Decacarbonyldihydridotriosmium
H2Os3(CO)10 2022.svg
Names
IUPAC names
Decacarbonyldihydridotriosmium,
Decacarbonyl-1κ3C,2κ3C,3κ4C-di-μ-hydrido-1:2κ2H;1:2κ2H-triangulo-triosmium(3 OsOs)
Identifiers
3D model (JSmol)
PubChem CID
  • InChI=1S/10CO.3Os.2H/c10*1-2;;;;;/q;;;;;;;;;;;2*+1;2*-1
    Key: ABHQEXNWCLZGFV-UHFFFAOYSA-N
  • [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
H2Os3(CO)10
Molar mass 852.81 g/mol
AppearanceDeep purple-violet crystals
Density 3.48 g/cm3
Boiling point decomposes
no
Solubility in other solventsreacts with Chlorocarbons
Structure
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).
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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.

Contents

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]

Related Research Articles

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<span class="mw-page-title-main">Metal carbonyl</span> Coordination complexes of transition metals with carbon monoxide ligands

Metal carbonyls are coordination complexes of transition metals with carbon monoxide ligands. Metal carbonyls are useful in organic synthesis and as catalysts or catalyst precursors in homogeneous catalysis, such as hydroformylation and Reppe chemistry. In the Mond process, nickel tetracarbonyl is used to produce pure nickel. In organometallic chemistry, metal carbonyls serve as precursors for the preparation of other organometallic complexes.

<span class="mw-page-title-main">Bridging ligand</span> Ligand which connects two or more (usually metal) atoms in a coordination complex

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Osmium compounds are compounds containing the element osmium (Os). Osmium forms compounds with oxidation states ranging from −2 to +8. The most common oxidation states are +2, +3, +4, and +8. The +8 oxidation state is notable for being the highest attained by any chemical element aside from iridium's +9 and is encountered only in xenon, ruthenium, hassium, iridium, and plutonium. The oxidation states −1 and −2 represented by the two reactive compounds Na
2
[Os
4
(CO)
13
]
and Na
2
[Os(CO)
4
]
are used in the synthesis of osmium cluster compounds.

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<span class="mw-page-title-main">Transition-metal allyl complex</span>

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<span class="mw-page-title-main">Phosphenium</span> Divalent cations of phosphorus

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<span class="mw-page-title-main">Lanthanocene</span>

A lanthanocene is a type of metallocene compound that contains an element from the lanthanide series. The most common lanthanocene complexes contain two cyclopentadienyl anions and an X type ligand, usually hydride or alkyl ligand.

<span class="mw-page-title-main">Transition metal chloride complex</span> Coordination complex

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<span class="mw-page-title-main">Transition metal thioether complex</span>

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Phosphanides are chemicals containing the [PH2] anion. This is also known as the phosphino anion or phosphido ligand. The IUPAC name can also be dihydridophosphate(1−).

<span class="mw-page-title-main">Transition metal ether complex</span>

In chemistry, a transition metal ether complex is a coordination complex consisting of a transition metal bonded to one or more ether ligand. The inventory of complexes is extensive. Common ether ligands are diethyl ether and tetrahydrofuran. Common chelating ether ligands include the glymes, dimethoxyethane (dme) and diglyme, and the crown ethers. Being lipophilic, metal-ether complexes often exhibit solubility in organic solvents, a property of interest in synthetic chemistry. In contrast, the di-ether 1,4-dioxane is generally a bridging ligand.

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