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.
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
Reactionsedit
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]
Referencesedit
^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.
January 01, 1970
decacarbonyldihydridotriosmium, organoosmium, compound, with, formula, h2os3, this, purple, violet, crystalline, stable, cluster, noteworthy, because, electron, deficient, hence, adds, variety, substrates, names, iupac, names, decacarbonyl, 1κ3c, 2κ3c, 3κ4c, h. 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 Decacarbonyldihydridotriosmium Names IUPAC names Decacarbonyldihydridotriosmium Decacarbonyl 1k3C 2k3C 3k4C wbr di m hydrido 1 2k2H 1 2k2H wbr 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 c10 1 2 q 2 1 2 1Key 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 Y N Infobox referencesStructure and synthesis editThe trinuclear cluster features an isosceles triangular array of metals with one short edge rOs Os 2 68 A which is spanned by the two hydride ligands and two longer edges rOs Os 2 81 A 1 It can be described as Os CO 4 Os CO 3 m 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 COReactions editThe cluster reacts with a wide range of reagents under mild conditions Illustrative is its reaction with diazomethane to give Os3 CO 10 m H m CH3 exhibiting an agostic interaction the first identified in a metal cluster 4 5 References edit 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 m hydrido decacarbonyltriosmium m 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 m Hydridotriosmium Os3 m 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 Retrieved from https en wikipedia org w index php title Decacarbonyldihydridotriosmium amp oldid 1187896586, wikipedia, wiki, book, books, library,
