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| ==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 | 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 = 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 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. | series = Inorganic Syntheses | isbn = 9780470132593}}</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 <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 | issue = 15}}</ref> | ||
| ==References== | ==References== | ||
Revision as of 11:15, 21 October 2011
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| Names | |
|---|---|
| IUPAC names
Decacarbonyldihydridotriosmium, decacarbonyl-1κC,2κC,3κC- di-μ-hydrido-1:2κH;1:2κH -triangulo-triosmium (3 Os—Os) | |
| Identifiers | |
| CAS Number | |
| 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 | no |
| Solubility in other solvents | decomp in Chlorocarbons |
| Structure | |
| Coordination geometry | triangular cluster |
| Hazards | |
| Occupational safety and health (OHS/OSH): | |
| Main hazards | Toxic |
| Related compounds | |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C , 100 kPa).
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Infobox references
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Decacarbonyldihydridotriosmium is a chemical compound with the formula H2Os3(CO)10. This purple-violet crystalline air-stable cluster is noteworthy because it is electronically unsaturated 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. 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 2 to give 3Os3(CO)9. With diazomethane, it gives Os3(CO)10(μ-H)(μ-CH3), exhibiting an agostic interaction, the first identified in a metal cluster.
References
- Melvyn Rowen Churchill, Frederick J. Hollander, and 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.
{{cite journal}}: CS1 maint: multiple names: authors list (link) - Kaesz, H. D.; Glavee, G. N.; Angelici, R. J. (1990). "Decacarbonyldi-μ-Hydridotriosmium: Os3(μ-H)2(CO)10". Inorganic Syntheses. Inorganic Syntheses. 28: 238–39. doi:10.1002/9780470132593.ch60. ISBN 9780470132593.
- 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.
| Osmium compounds | |||
|---|---|---|---|
| Os(0) | |||
| Os(0,I) | |||
| Os(I) | |||
| Os(I,II) | |||
| Os(II) |
| ||
| Os(III) | |||
| Os(IV) | |||
| Os(V) | |||
| Os(VI) | |||
| Os(VII) |
| ||
| Os(VIII) | |||