| Revision as of 06:55, 11 August 2011 editLightbot (talk | contribs)791,863 edits mostly units← Previous edit |
Latest revision as of 08:40, 12 July 2024 edit undoJWBE (talk | contribs)Extended confirmed users10,126 edits added Category:Chemical compounds containing metal–metal bonds using HotCat |
| (38 intermediate revisions by 22 users not shown) |
| Line 1: |
Line 1: |
|
{{chembox |
|
{{chembox |
|
|
| Watchedfields = changed |
|
| verifiedrevid = 403475349 |
|
| verifiedrevid = 444218252 |
|
| ImageFile = Os3(CO)12.png |
|
|
⚫ |
| ImageFile1 = Triosmiumdodecacarbonyl.svg |
|
| ImageSize = 200px |
|
|
|
| ImageSize1 = |
| ⚫ |
| IUPACName = ''cyclo''-tris(tetracarbonylosmium)<br />(3 ''Os''—''Os'') |
|
|
|
| ImageFile2 = Triosmium-dodecacarbonyl-from-xtal-3D-bs-17.png |
| ⚫ |
| OtherNames = Osmium carbonyl |
|
|
|
| ImageSize2 = |
| ⚫ |
| Section1 = {{Chembox Identifiers |
|
|
|
| ImageFile3 = Os3(CO)12sample (cropped).jpg |
|
| SMILES = |
|
|
|
| ImageSize3 = |
| ⚫ |
| CASNo = 15696-40-9 |
|
|
⚫ |
| IUPACName = ''cyclo''-tris(tetracarbonylosmium)<wbr />(3 ''Os''—''Os'') |
|
⚫ |
| OtherNames = Osmium carbonyl |
|
⚫ |
|Section1={{Chembox Identifiers |
|
|
| CASNo_Ref = {{cascite|correct|??}} |
|
⚫ |
| CASNo = 15696-40-9 |
|
|
| ChemSpiderID = 452847 |
|
|
| PubChem = 6096995 |
|
|
| StdInChI=1S/12CO.3Os/c12*1-2;;; |
|
|
| StdInChIKey = VUBLMKVEIPBYME-UHFFFAOYSA-N |
|
|
| SMILES = #.#.#.#.#.#.#.#.#.#.#.#... |
|
}} |
|
}} |
|
| Section2 = {{Chembox Properties |
|
|Section2={{Chembox Properties |
|
| Formula = C<sub>12</sub>O<sub>12</sub>Os<sub>3</sub> |
|
| Formula = C<sub>12</sub>O<sub>12</sub>Os<sub>3</sub> |
|
| MolarMass = 906.81 g/mol |
|
| MolarMass = 906.81 g/mol |
|
| Appearance = yellow solid |
|
| Appearance = yellow solid |
|
| Density = 3.48 g/cm<sup>3</sup> |
|
| Density = 3.48 g/cm<sup>3</sup> |
|
| Solubility = insoluble |
|
| Solubility = insoluble |
|
| Solvent = other solvents |
|
| Solvent = other solvents |
|
| SolubleOther = slightly in organic solvents |
|
| SolubleOther = slightly in organic solvents |
|
| MeltingPt = 224 °C |
|
| MeltingPtC = 224 |
|
| BoilingPt = sublimes in vacuum |
|
| BoilingPt = sublimes in vacuum |
|
}}<!-- |
|
}}<!-- |
|
|
|
|
| Line 25: |
Line 35: |
|
|- |
|
|- |
|
--> |
|
--> |
|
| Section3 = {{Chembox Structure |
|
|Section3={{Chembox Structure |
|
| CrystalStruct = |
|
| CrystalStruct = |
|
| Dipole = 0 ] (0 ]·m) |
|
| Dipole = 0 ] (0 ]·m) |
|
}} |
|
}} |
|
| Section7 = {{Chembox Hazards |
|
|Section7={{Chembox Hazards |
|
| ExternalMSDS = |
|
| ExternalSDS = |
|
| MainHazards = CO source |
|
| MainHazards = CO source |
|
|
| GHSPictograms = {{GHS06}}{{GHS07}} |
|
| RPhrases = 22-36/37/38 |
|
|
|
| GHSSignalWord = Danger |
|
| SPhrases = 22-26-36/37/39 |
|
|
|
| HPhrases = {{H-phrases|301|302|315|319|330|335}} |
|
|
| PPhrases = {{P-phrases|261|264|270|271|280|301+312|302+352|304+340|305+351+338|312|321|330|332+313|337+313|362|403+233|405|501}} |
|
}} |
|
}} |
|
| Section8 = {{Chembox Related |
|
|Section8={{Chembox Related |
|
| OtherCpds = ]<br />]<br />] |
|
| OtherCompounds = ]<br />]<br />] |
|
}} |
|
}} |
|
}} |
|
}} |
|
|
|
|
|
'''Triosmium dodecacarbonyl''' is a ] with the formula Os<sub>3</sub>(CO)<sub>12</sub>. This yellow-colored ] is an important precursor to ]. Many of the advances in cluster chemistry have arisen from studies on derivatives of Os<sub>3</sub>(CO)<sub>12</sub> and its lighter analogue ]. |
|
'''Triosmium dodecacarbonyl''' is a ] with the formula Os<sub>3</sub>(CO)<sub>12</sub>. This yellow-colored ] is an important precursor to ]. Many of the advances in cluster chemistry have arisen from studies on derivatives of Os<sub>3</sub>(CO)<sub>12</sub> and its lighter analogue ]. |
|
|
|
|
|
==Structure and synthesis== |
|
==Structure and synthesis== |
|
The cluster has D<sub>3h</sub> ], consisting of an ] of Os atoms, each of which bears two axial and two equatorial ] ]s. The Os–Os bond distance is 2.88 Â (288 pm).<ref>Corey, E. R.; Dahl, L. F. “The Molecular and Crystal Structure of Os<sub>3</sub>(CO)<sub>12</sub>” Inorganic Chemistry 1962, volume 1, pages 521 - 526. DOI: 10.1021/ic50003a016</ref> Ru<sub>3</sub>(CO)<sub>12</sub> has the same structure, whereas Fe<sub>3</sub>(CO)<sub>12</sub> is different, with two bridging CO ligands resulting in C<sub>2v</sub> symmetry. |
|
The cluster has D<sub>3h</sub> ], consisting of an ] of Os atoms, each of which bears two axial and two equatorial ] ]s. Each of the three osmium centers has an octahederal structure with four CO ligands and the other two osmium atoms. |
|
|
|
|
|
|
The Os–Os bond distance is 2.88 Å (288 pm).<ref>Corey, E. R.; Dahl, L. F. "The Molecular and Crystal Structure of Os<sub>3</sub>(CO)<sub>12</sub>" Inorganic Chemistry 1962, volume 1, pages 521–526; {{doi|10.1021/ic50003a016}}.</ref><ref>{{ cite journal | title = Structural studies on polynuclear osmium carbonyl hydrides. 1. Crystal structures of the isomorphous species H<sub>2</sub>Os<sub>3</sub>(CO)<sub>11</sub> and Os<sub>3</sub>(CO)<sub>12</sub>. Role of an equatorial ''μ''<sub>2</sub>-bridging hydride ligand in perturbing the arrangement of carbonyl ligands in a triangular cluster | first1 = Melvyn Rowen | last1 = Churchill | first2 = Barry G. | last2 = DeBoer | journal = ] | year = 1977 | volume = 16 | issue = 4 | pages = 878–884 | doi = 10.1021/ic50170a032 }}</ref> Ru<sub>3</sub>(CO)<sub>12</sub> has the same structure, whereas Fe<sub>3</sub>(CO)<sub>12</sub> is different, with two bridging CO ligands resulting in C<sub>2v</sub> symmetry. In solution, {{chem2|Os3(CO)12}} is fluxional as indicated by <sup>13</sup>C NMR measurements. The barrier is estimated at 70 kJ/mol<ref>{{cite journal |doi=10.1039/A608514H |title=Dynamics and Fluxionality in Metal Carbonyl Clusters: Some Old and New Problems |date=1997 |last1=Farrugia |first1=Louis J. |journal=Journal of the Chemical Society, Dalton Transactions |issue=11 |pages=1783–1792 }}</ref> |
| ⚫ |
Os<sub>3</sub>(CO)<sub>12</sub> is prepared by the direct reaction of ] with carbon monoxide at 175 °C:<ref>Drake, S. R.; Loveday, P. A. “Dodecarbonyltriosmium” Inorganic Syntheses, 1990, volume 28, pages 230-1. ISBN 0-471-52619-3.</ref> |
|
|
|
|
| ⚫ |
: 3 OsO<sub>4</sub> + 24 CO → Os<sub>3</sub>(CO)<sub>12</sub> + 12 CO<sub>2</sub> |
|
|
⚫ |
Os<sub>3</sub>(CO)<sub>12</sub> is prepared by the direct reaction of ] with carbon monoxide at 175 °C under high pressures:<ref>Drake, S. R.; Loveday, P. A. "Dodecarbonyltriosmium" Inorganic Syntheses, 1990, volume 28, pages 230–231. {{ISBN|0-471-52619-3}}.</ref> |
|
⚫ |
: 3 OsO<sub>4</sub> + 24 CO → Os<sub>3</sub>(CO)<sub>12</sub> + 12 CO<sub>2</sub> |
|
The yield is nearly quantitative. |
|
The yield is nearly quantitative. |
|
|
|
|
|
==Reactions== |
|
==Reactions== |
|
The chemical properties of Os<sub>3</sub>(CO)<sub>12</sub> have been thoroughly examined. Direct reactions of ligands with the cluster often lead to complex product distributions because the inert Os–CO bonds require high temperatures to break, and at such high temperatures successive the initially formed adducts react further. More successfully, Os<sub>3</sub>(CO)<sub>12</sub> is converted to more labile derivatives such as Os<sub>3</sub>(CO)<sub>11</sub>(]) and Os<sub>3</sub>(CO)<sub>10</sub>(MeCN)<sub>2</sub> using ] as a decarbonylating agent.<ref>Nicholls, J. N.; Vargas, M. D. “Some Useful Derivatives of Dodecarbonyltriosmium” Inorganic Syntheses, 1990, volume 28, pages 232-5. ISBN 0-471-52619-3.</ref> Os<sub>3</sub>(CO)<sub>11</sub>(MeCN) reacts with a variety of even weakly basic ligands to form adducts such as Os<sub>3</sub>(CO)<sub>11</sub>(]) and Os<sub>3</sub>(CO)<sub>11</sub>(]). The direct reaction of Os<sub>3</sub>(CO)<sub>12</sub> with ethylene and pyridine results in degradation of these organic ligands to give the ] hydride HOs<sub>3</sub>(CO)<sub>10</sub>(]<sup>1</sup>,η<sup>2</sup>-C<sub>2</sub>H<sub>3</sub>) and the pyridyl-hydride HOs<sub>3</sub>(CO)<sub>10</sub>(NC<sub>5</sub>H<sub>4</sub>). These products illustrate the stability of Os–H and Os–C bonds. |
|
Many chemical reactions of Os<sub>3</sub>(CO)<sub>12</sub> have been examined. Direct reactions of ligands with the cluster often lead to complex product distributions. Os<sub>3</sub>(CO)<sub>12</sub> converts to more labile derivatives such as Os<sub>3</sub>(CO)<sub>11</sub>(]) and Os<sub>3</sub>(CO)<sub>10</sub>(MeCN)<sub>2</sub> using ] as a decarbonylating agent:<ref>Nicholls, J. N.; Vargas, M. D. "Some Useful Derivatives of Dodecarbonyltriosmium" Inorganic Syntheses, 1990, volume 28, pages 232–235. {{ISBN|0-471-52619-3}}.</ref> |
|
|
:{{chem2|Os3(CO)12 + (CH3)3NO + CH3CN → Os3(CO)11(CH3CN) + CO2 + (CH3)3N}} |
|
|
:{{chem2|Os3(CO)11(CH3CN) + (CH3)3NO + CH3CN → Os3(CO)10(CH3CN)2 + CO2 + (CH3)3N}} |
|
|
|
|
|
|
Os<sub>3</sub>(CO)<sub>11</sub>(MeCN) reacts with a variety of even weakly basic ligands to form adducts. |
|
Os<sub>3</sub>(CO)<sub>12</sub> is a platform to examine the ways that hydrocarbons can interact with ensembles of metals. For example, the molecule CH<sub>3</sub>(H)Os<sub>3</sub>(CO)<sub>10</sub> provided one of the first clear-cut examples of ].<ref>Calvert, R. B.; Shapley, J. R. “Decacarbonyl(methyl)hydrotriosmium: NMR evidence for a Carbon<sup>..</sup>Hydrogen<sup>..</sup>Osmium Interaction” Journal of the American Chemical Society 1978, volume 100, pages 7726-7. DOI: 10.1021/ja00492a047</ref> |
|
|
|
|
|
|
|
Purging a solution of triosmium dodecacarbonyl in boiling ] (or similar inert solvent of similar boiling point) with ] gives the dihydride ]:<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 = 9780471526193 }}</ref> |
|
From the perspective of ], the molecule ] is noteworthy. In this compound, the two hydride ligands bridge one Os-Os edge. The molecule displays reactivity reminiscent of ].<ref>Keister, J. B.; Shapley, J. R. “Solution Structures and Dynamics of complexes of Decacarbonyldihydrotriosmium with Lewis Bases” Inorganic Chemistry 1982, volume 21, pages 3304-10.DOI: 10.1021/ic00139a011</ref> |
|
|
|
:{{chem2|Os3(CO)12 + H2 → Os3H2(CO)10 + 2 CO}} |
|
|
|
|
|
] is obtained by treating solid triosmium dodecacarbonyl with 200 atmospheres of ] at 280-290 °C.<ref name=RKP>{{cite journal |doi=10.1021/om00077a026|title=Properties of the Pentacarbonyls of Ruthenium and Osmium|year=1983|last1=Rushman|first1=Paul|last2=Van Buuren|first2=Gilbert N.|last3=Shiralian|first3=Mahmoud|last4=Pomeroy|first4=Roland K.|journal=Organometallics|volume=2|issue=5|pages=693–694}}</ref> |
|
|
:{{chem2|Os3(CO)12 + 3 CO → 3 Os(CO)5}} |
|
|
|
|
|
==References== |
|
==References== |
| Line 64: |
Line 84: |
|
] |
|
] |
|
] |
|
] |
|
|
] |
|
|
|
| ⚫ |
] |
|