Names | |
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IUPAC name cyclo-tris(tetracarbonylruthenium) | |
Other names Ruthenium carbonyl | |
Identifiers | |
3D model (JSmol) | |
ChemSpider | |
ECHA InfoCard | 100.035.701 |
EC Number |
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PubChem CID | |
CompTox Dashboard (EPA) | |
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Properties | |
C12O12Ru3 | |
Molar mass | 639.33 g/mol |
Appearance | orange solid |
Density | 2.48 g/cm3 |
Melting point | 224 °C (435 °F; 497 K) |
Boiling point | sublimes in vacuum |
insoluble | |
Solubility in organic solvents | soluble |
Structure | |
D3h cluster | |
0 D | |
Hazards | |
Occupational safety and health (OHS/OSH): | |
Main hazards | Toxic, CO Source |
GHS labelling: | |
Warning | |
H302, H315, H319, H332, H335 | |
P261, P264, P270, P271, P280, P301+P312, P302+P352, P304+P312, P304+P340, P305+P351+P338, P312, P321, P330, P332+P313, P337+P313, P362, P403+P233, P405, P501 | |
Related compounds | |
Related compounds | Triiron dodecacarbonyl Triosmium dodecacarbonyl |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). |
Triruthenium dodecacarbonyl is the chemical compound with the formula Ru3(CO)12. Classified as metal carbonyl cluster, it is a dark orange-colored solid that is soluble in nonpolar organic solvents. The compound serves as a precursor to other organoruthenium compounds.
The cluster has D3h symmetry, consisting of an equilateral triangle of Ru atoms, each of which bears two axial and two equatorial CO ligands. The Ru-Ru distance is 284 pm. [1] Os3(CO)12 has the same structure. In Fe3(CO)12, two CO ligands are bridging, resulting in C2v symmetry. In solution, Ru3(CO)12 is fluxional as indicated by the observation of a single CO signal in the room temperature 13C NMR spectrum. The barrier is estimated at 20 kJ/mol [2]
Ru3(CO)12 is prepared by treating solutions of ruthenium trichloride with carbon monoxide in the presence of a base. Dichlororuthenium tricarbonyl dimer is an intermediate. [3] [4] The stoichiometry of the reaction is uncertain, one possibility being the following:
The chemical properties of Ru3(CO)12 have been widely studied, and the cluster has been converted to hundreds of derivatives. High pressures of CO convert the cluster to the monomeric ruthenium pentacarbonyl, which reverts to the parent cluster upon standing.
The instability of Ru(CO)5 contrasts with the robustness of the corresponding Fe(CO)5. The condensation of Ru(CO)5 into Ru3(CO)12 proceeds via initial, rate-limiting loss of CO to give the unstable, coordinatively unsaturated species Ru(CO)4. This tetracarbonyl binds Ru(CO)5, initiating the condensation. [5]
Upon warming under a pressure of hydrogen, Ru3(CO)12 converts to the tetrahedral cluster H4Ru4(CO)12. [6] Ru3(CO)12 undergoes substitution reactions with Lewis bases:
where L is a tertiary phosphine or an isocyanide. It forms complexes with acenaphthylene. [7]
Ru3(CO)12 forms a variety of alkene complexes, some where the Ru3 core remains intact but often with fragmentation. Upon treatment with 1,5-cyclooctadiene gives the monoRu tricarbonyl derivative: [8]
Upon irradiation with UV light, Ru3(CO)12 converts to an insoluble polymeric form. [9]
At high temperatures, Ru3(CO)12 converts to a series of clusters that contain interstitial carbido ligands. These include Ru6C(CO)17 and Ru5C(CO)15. Anionic carbido clusters are also known, including [Ru5C(CO)14]2− and the bioctahedral cluster [Ru10C2(CO)24]2−. [10] Ru3(CO)12 -derived carbido compounds have been used to synthesize nanoparticles for catalysis. These particles consist of 6-7 atoms and thus are all surface, resulting in extraordinary activity.
Iron pentacarbonyl, also known as iron carbonyl, is the compound with formula Fe(CO)5. Under standard conditions Fe(CO)5 is a free-flowing, straw-colored liquid with a pungent odour. Older samples appear darker. This compound is a common precursor to diverse iron compounds, including many that are useful in small scale organic synthesis.
Ruthenium(III) chloride is the chemical compound with the formula RuCl3. "Ruthenium(III) chloride" more commonly refers to the hydrate RuCl3·xH2O. Both the anhydrous and hydrated species are dark brown or black solids. The hydrate, with a varying proportion of water of crystallization, often approximating to a trihydrate, is a commonly used starting material in ruthenium chemistry.
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.
Triiron dodecacarbonyl is the organoiron compound with the formula Fe3(CO)12. It is a dark green solid that sublimes under vacuum. It is soluble in nonpolar organic solvents to give intensely green solutions. Most low-nuclearity clusters are pale yellow or orange. Hot solutions of Fe3(CO)12 decompose to an iron mirror, which can be pyrophoric in air. The solid decomposes slowly in air, and thus samples are typically stored cold under an inert atmosphere. It is a more reactive source of iron(0) than iron pentacarbonyl.
Triosmium dodecacarbonyl is a chemical compound with the formula Os3(CO)12. This yellow-colored metal carbonyl cluster is an important precursor to organo-osmium compounds. Many of the advances in cluster chemistry have arisen from studies on derivatives of Os3(CO)12 and its lighter analogue Ru3(CO)12.
Tetrarhodium dodecacarbonyl is the chemical compound with the formula Rh4(CO)12. This dark-red crystalline solid is the smallest binary rhodium carbonyl that can be handled as a solid under ambient conditions. It is used as a catalyst in organic synthesis.
Cyclopentadienylmolybdenum tricarbonyl dimer is the chemical compound with the formula Cp2Mo2(CO)6, where Cp is C5H5. A dark red solid, it has been the subject of much research although it has no practical uses.
Organoiron chemistry is the chemistry of iron compounds containing a carbon-to-iron chemical bond. Organoiron compounds are relevant in organic synthesis as reagents such as iron pentacarbonyl, diiron nonacarbonyl and disodium tetracarbonylferrate. Although iron is generally less active in many catalytic applications, it is less expensive and "greener" than other metals. Organoiron compounds feature a wide range of ligands that support the Fe-C bond; as with other organometals, these supporting ligands prominently include phosphines, carbon monoxide, and cyclopentadienyl, but hard ligands such as amines are employed as well.
Organoruthenium chemistry is the chemistry of organometallic compounds containing a carbon to ruthenium chemical bond. Several organoruthenium catalysts are of commercial interest and organoruthenium compounds have been considered for cancer therapy. The chemistry has some stoichiometric similarities with organoiron chemistry, as iron is directly above ruthenium in group 8 of the periodic table. The most important reagents for the introduction of ruthenium are ruthenium(III) chloride and triruthenium dodecacarbonyl.
The Shvo catalyst is an organoruthenium compound that catalyzes the hydrogenation of polar functional groups including aldehydes, ketones and imines. The compound is of academic interest as an early example of a catalyst for transfer hydrogenation that operates by an "outer sphere mechanism". Related derivatives are known where p-tolyl replaces some of the phenyl groups. Shvo's catalyst represents a subset of homogeneous hydrogenation catalysts that involves both metal and ligand in its mechanism.
Iron tetracarbonyl dihydride is the organometallic compound with the formula H2Fe(CO)4. This compound was the first transition metal hydride discovered. The complex is stable at low temperatures but decomposes rapidly at temperatures above –20 °C.
Half sandwich compounds, also known as piano stool complexes, are organometallic complexes that feature a cyclic polyhapto ligand bound to an MLn center, where L is a unidentate ligand. Thousands of such complexes are known. Well-known examples include cyclobutadieneiron tricarbonyl and (C5H5)TiCl3. Commercially useful examples include (C5H5)Co(CO)2, which is used in the synthesis of substituted pyridines, and methylcyclopentadienyl manganese tricarbonyl, an antiknock agent in petrol.
In chemistry, a metal carbonyl cluster is a compound that contains two or more metal atoms linked in part by metal–metal bonds and containing carbon monoxide (CO) as the exclusive or predominant ligand. The area is a subfield of metal carbonyl chemistry, and many metal carbonyl clusters are in fact prepared from simple metal carbonyls. Simple examples include Fe2(CO)9, Fe3(CO)12, and Mn2(CO)10. High nuclearity clusters include [Rh13(CO)24H3]2− and the stacked Pt3 triangules [Pt3n(CO)6n]2− (n = 2–6).
Ruthenium pentacarbonyl is the organoruthenium compound with the formula Ru(CO)5. It is a colorless, light-sensitive liquid that readily decarbonylates upon standing at room temperature. It is of academic interest as an intermediate for the synthesis of metal carbonyl complexes.
Metal arene complexes are organometallic compounds of the formula (C6R6)xMLy. Common classes are of the type (C6R6)ML3 and (C6R6)2M. These compounds are reagents in inorganic and organic synthesis. The principles that describe arene complexes extend to related organic ligands such as many heterocycles (e.g. thiophene) and polycyclic aromatic compounds (e.g. naphthalene).
Tricarbonylbis(triphenylphosphine)iron(0) is a coordination complex with the formula Fe(CO)3(PPh3)2 (Ph = C6H5). A yellow solid, this complex is derived from iron pentacarbonyl by replacement of two carbonyl ligands by triphenylphosphine (PPh3).
(Triphenylphosphine)iron tetracarbonyl is a coordination complex with the formula Fe(CO)4(PPh3) (Ph = C6H5). An off-white solid, this complex is derived from iron pentacarbonyl by replacement of one carbonyl ligand by triphenylphosphine (PPh3).
Dichlororuthenium tricarbonyl dimer is an organoruthenium compound with the formula [RuCl2(CO)3]2. A yellow solid, the molecule features a pair of octahedral Ru centers bridged by a pair of chloride ligands. The complex is a common starting material in ruthenium chemistry.
In organometallic chemistry, (diene)iron tricarbonyl describes a diverse family of related coordination complexes consisting of a diene ligand coordinated to a Fe(CO)3 center. Often the diene is conjugated, e.g., butadiene, but the family includes nonconjugated dienes as well. The compounds are yellow, air-stable, often low-melting, and soluble in hydrocarbon solvents. The motif is so robust that even unstable dienes form easily characterized derivatives, such as norbornadienone and cyclobutadiene.
Tris(cyclooctatetraene)triiron or Fe3(COT)3, also referred to as the Lavallo-Grubbs compound (after its discoverers) is an organoiron compound with the formula Fe3(C8H8)3. It is a pyrophoric, black crystalline solid, which is insoluble in common organic solvents.The compound represents a rare example of a hydrocarbon analogue of the well-known Triiron dodecacarbonyl (Fe3(CO)12), originally prepared by Dewar and Jones in the early 20th century.