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{{chembox {{chembox
| Watchedfields = changed
| verifiedrevid = 394839838 | verifiedrevid = 428743017
| Name = Decacarbonyldihydridotriosmium | Name = Decacarbonyldihydridotriosmium
| ImageFile = H2Os3(CO)10.png
| ImageFile = H2Os3(CO)10 2022.svg
| ImageSize = 250px
| ImageName = | ImageSize = 200px
| ImageName =
| IUPACName = Decacarbonyldihydridotriosmium, <br />decacarbonyl-1κ<sup>3</sup>''C'',2κ<sup>3</sup>''C'',3κ<sup>4</sup>''C''-<br />di-μ-hydrido-1:2κ<sup>2</sup>''H'';1:2κ<sup>2</sup>''H''<br />-''triangulo''-triosmium (3 ''Os''—''Os'') | IUPACName = Decacarbonyldihydridotriosmium,<br />Decacarbonyl-1κ<sup>3</sup>''C'',2κ<sup>3</sup>''C'',3κ<sup>4</sup>''C''-<wbr />di-μ-hydrido-1:2κ<sup>2</sup>''H'';1:2κ<sup>2</sup>''H''<wbr />-''triangulo''-triosmium(3 ''Os''—''Os'')
| OtherNames =
| OtherNames =
| Section1 = {{Chembox Identifiers | Section1 = {{Chembox Identifiers
⚫ | CASNo = 41766-80-7
| CASNo_Ref = {{cascite|correct|??}}
⚫ | RTECS =
⚫ | CASNo = 41766-80-7
| PubChem = 139143320
⚫ | RTECS =
| StdInChI=1S/10CO.3Os.2H/c10*1-2;;;;;/q;;;;;;;;;;;2*+1;2*-1
| StdInChIKey = ABHQEXNWCLZGFV-UHFFFAOYSA-N
| SMILES = ..#.#.#.#.#.#.#.#.#.#...
}} }}
| Section2 = {{Chembox Properties | Section2 = {{Chembox Properties
| Formula = H<sub>2</sub>Os<sub>3</sub>(CO)<sub>10</sub> | Formula = H<sub>2</sub>Os<sub>3</sub>(CO)<sub>10</sub>
| MolarMass = 852.81 g/mol | MolarMass = 852.81 g/mol
| Appearance = Deep purple-violet crystals | Appearance = Deep purple-violet crystals
| Density = 3.48 g/cm<small>3</small> | Density = 3.48 g/cm<small>3</small>
| Solubility = no | Solubility = insoluble
| Solvent = other solvents | Solvent = other solvents
| SolubleOther = decomp in ] | SolubleOther = reacts with ]s
| MeltingPt = | MeltingPt =
| BoilingPt = decomposes | BoilingPt = decomposes
}} }}
| Section3 = {{Chembox Structure | Section3 = {{Chembox Structure
| Coordination = triangular cluster | Coordination = triangular cluster
| CrystalStruct = | CrystalStruct =
| Dipole = | Dipole =
}} }}
| Section7 = {{Chembox Hazards | Section7 = {{Chembox Hazards
| ExternalMSDS = | ExternalSDS =
| MainHazards = Toxic | MainHazards = Toxic
| RPhrases =
| SPhrases =
}} }}
| Section8 = {{Chembox Related | Section8 = {{Chembox Related
| OtherCpds = ] | OtherCompounds = ]
}} }}
}} }}


'''Decacarbonyldihydridotriosmium''' is a ] with the formula H<sub>2</sub>Os<sub>3</sub>(CO)<sub>10</sub>. This purple-violet ] air-stable cluster is noteworthy because it is ] and hence adds a variety of substrates. '''Decacarbonyldihydridotriosmium''' is an ] with the formula H<sub>2</sub>Os<sub>3</sub>(CO)<sub>10</sub>. This purple-violet ] air-stable cluster is noteworthy because it is ] and hence adds a variety of substrates.


==Structure and synthesis== ==Structure and synthesis==
The trinuclear cluster features an isosceles triangular array of metals with one short edge (''r''<sub>Os-Os</sub> = 2.68 Å), which is spanned by the two hydride ligands, and two longer edges (r<sub>Os-Os</sub> = 2.81 Å).<ref>{{cite journal | author = Melvyn Rowen Churchill, Frederick J. Hollander, and John P. Hutchinson | title = Structural studies on polynuclear osmium carbonyl hydrides. 5.Crystal structure and molecular geometry of di-μ-hydrido-decacarbonyltriosmium, (μ-H)<sub>2</sub>Os<sub>3</sub>(CO)<sub>10</sub> | year = 1977 | journal = ] | volume = 28 | issue = | pages = 2697–2700 | doi = 10.1021/ic50177a006}}</ref> It can be described as Os(CO)<sub>4</sub><sub>2</sub>. The bonding in the Os<sub>2</sub>H<sub>2</sub> subunit has been compared to the 3-center, 2e bonding in diborane. It is prepared by purging a solution of ] in ] (or other inert solvent of similar boiling point) with ].<ref>{{cite journal | author = Kaesz, H. D. | title = Decacarbonyldi-μ-Hydridotriosmium: Os<sub>3</sub>(μ-H)<sub>2</sub>(CO)<sub>10</sub> | year = 1990 | journal = ] | volume = 28 | pages = 238–39| doi = 10.1002/9780470132593.ch60 | last2 = Glavee | first2 = G. N. | last3 = Angelici | first3 = R. J.}}</ref> The trinuclear cluster features an isosceles triangular array of metals with one short edge (''r''<sub>Os-Os</sub> = 2.68 Å), which is spanned by the two hydride ligands, and two longer edges (r<sub>Os-Os</sub> = 2.81 Å).<ref>{{cite journal |author1=Melvyn Rowen Churchill |author2=Frederick J. Hollander |author3=John P. Hutchinson | title = Structural studies on polynuclear osmium carbonyl hydrides. 5.Crystal structure and molecular geometry of di-μ-hydrido-decacarbonyltriosmium, (μ-H)<sub>2</sub>Os<sub>3</sub>(CO)<sub>10</sub> | year = 1977 | journal = ] | volume = 28 | issue = 11| pages = 2697–2700 | doi = 10.1021/ic50177a006}}</ref> It can be described as Os(CO)<sub>4</sub><sub>2</sub>. The bonding in the Os<sub>2</sub>H<sub>2</sub> subunit has been compared to the ] in ]. The molecule forms a variety of adducts with loss of H<sub>2</sub>.<ref>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}}.</ref>
It is prepared by purging a solution of ] in ] (or other inert solvent of similar boiling point) with ].<ref>{{cite book | author = Kaesz, H. D. | title = Decacarbonyldi-μ-Hydridotriosmium: Os<sub>3</sub>(μ-H)<sub>2</sub>(CO)<sub>10</sub> | chapter = Decacarbonyldi-μ-Hydridotriosmium: Os <sub>3</sub> (μ-H) <sub>2</sub> (Co) <sub>10</sub> | year = 1990 | volume = 28 | pages = 238–39| doi = 10.1002/9780470132593.ch60 | series = Inorganic Syntheses| isbn = 978-0-471-52619-3 }}</ref>
:Os<sub>3</sub>(CO)<sub>12</sub> + H<sub>2</sub> → Os<sub>3</sub>H<sub>2</sub>(CO)<sub>10</sub> + 2 CO :Os<sub>3</sub>(CO)<sub>12</sub> + H<sub>2</sub> → Os<sub>3</sub>H<sub>2</sub>(CO)<sub>10</sub> + 2 CO


==Reactions== ==Reactions==
The cluster reacts with a wide range of reagents under mild conditions. Illustrative is its reaction with <sub>2</sub> to give <sub>3</sub>Os<sub>3</sub>(CO)<sub>9</sub>. With ], it gives Os<sub>3</sub>(CO)<sub>10</sub>(μ-H)(μ-CH<sub>3</sub>), exhibiting an ], the first identified in a metal cluster.<ref>{{cite journal | author = R. Bruce Calvert, John R. Shapley | title = 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 = ] | year = 1977 | volume = 99 | pages = 5225–5226 | doi = 10.1021/ja00457a077}}</ref> The cluster reacts with a wide range of reagents under mild conditions. Illustrative is its reaction with ] to give Os<sub>3</sub>(CO)<sub>10</sub>(μ-H)(μ-CH<sub>3</sub>), exhibiting an ], the first identified in a metal cluster.<ref>{{cite journal |doi=10.1021/ja00457a077|title=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 |year=1977 |last1=Calvert |first1=R. Bruce |last2=Shapley |first2=John R. |journal=Journal of the American Chemical Society |volume=99 |issue=15 |pages=5225–5226 |bibcode=1977JAChS..99.5225C }}</ref><ref>{{cite journal |doi=10.1021/ja00492a047|title= Decacarbonyl(methyl)hydrotriosmium: NMR Evidence for a Carbon<sup>...</sup>Hydrogen<sup>...</sup>Osmium Interaction |year=1978 |last1=Calvert |first1=R. Bruce |last2=Shapley |first2=John R. |journal=Journal of the American Chemical Society |volume=100 |issue=24 |pages=7726–7727 }}</ref>


==References== ==References==
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Latest revision as of 08:46, 9 December 2024

Decacarbonyldihydridotriosmium
Names
IUPAC names Decacarbonyldihydridotriosmium,
Decacarbonyl-1κC,2κC,3κC-di-μ-hydrido-1:2κH;1:2κH-triangulo-triosmium(3 Os—Os)
Identifiers
CAS Number
3D model (JSmol)
PubChem CID
InChI
  • InChI=1S/10CO.3Os.2H/c10*1-2;;;;;/q;;;;;;;;;;;2*+1;2*-1Key: ABHQEXNWCLZGFV-UHFFFAOYSA-N
SMILES
  • ..#.#.#.#.#.#.#.#.#.#...
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 , 100 kPa). checkY verify (what is  ?) 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 (rOs-Os = 2.68 Å), which is spanned by the two hydride ligands, and two longer edges (rOs-Os = 2.81 Å). It can be described as Os(CO)42. 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.

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

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.

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: Os 3 (μ-H) 2 (Co) 10". Decacarbonyldi-μ-Hydridotriosmium: Os3(μ-H)2(CO)10. Inorganic Syntheses. Vol. 28. pp. 238–39. doi:10.1002/9780470132593.ch60. ISBN 978-0-471-52619-3.
  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. Bibcode:1977JAChS..99.5225C. doi:10.1021/ja00457a077.
  5. Calvert, R. Bruce; Shapley, John R. (1978). "Decacarbonyl(methyl)hydrotriosmium: NMR Evidence for a CarbonHydrogenOsmium Interaction". Journal of the American Chemical Society. 100 (24): 7726–7727. doi:10.1021/ja00492a047.
Osmium compounds
Os(0)
Os(0,I)
Os(I)
Os(I,II)
Os(II)
Organoosmium(II) compounds
  • Os(C5H5)2
    • Os(III)
    Os(IV)
    Os(V)
    Os(VI)
    Os(VII)
    Os(VIII)
    Categories: