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Ruthenium Pentacarbonyl
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. Preparation Ru(CO)5 was originally prepared by carbonylation of ruthenium salts in the presence of a reducing agent.W. Manchot, Wilhelm J. Manchot "Darstellung von Rutheniumcarbonylen und -nitrosylen" Zeitschrift für Anorganische und Allgemeine Chemie 1936, volume 226, pp. 385-415. A more recent preparation involves photolysis of triruthenium dodecacarbonyl in the presence of carbon monoxide:Adams, R. D.; Barnard, T. S.; Cortopassi, J. E.; Wu, W.; Li, Z. "Platinum-ruthenium carbonyl cluster complexes" Inorganic Syntheses 1998, volume 32, pp. 280-284. :Ru3(CO)12 + 3 CO 3 Ru(CO)5 It is characterized by two intense νCO bands in the IR spectrum at 2038 and 2003 cm−1 (hexane solution). Co ...
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Organoruthenium Compound
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. In its organometallic compounds, ruthenium is known to adopt oxidation states from -2 ( u(CO)4sup>2−) to +6 ( uN(Me)4sup>−). Most common are those in the 2+ oxidation state, as illustrated below. File:Grubbs Catalyst 1st Generation.svg, 1st generation Grubbs catalyst File:ShvoCat.png, Shvo catalyst File:RuCymCl2.png, (cymene)ruthenium dichloride dimer File:Trirutheniumdodecacarbonyl.svg, triruthenium dodecacarbonyl. File:Chloro(cyclopentadienyl)bis(triphenylphos ...
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Decarbonylation
Decarbonylation is a type of organic reaction that involves loss of CO. It is often an undesirable reaction since it represents a degradation. In the chemistry of metal carbonyls, decarbonylation describes a substitution process, whereby a CO ligand is replaced by another ligand. Organic chemistry In the absence of metal catalysts, decarbonylation (vs decarboxylation) is rarely observed in organic chemistry. One exception is the decarbonylation of formic acid: :HCO2H → CO + H2O The reaction is induced by sulfuric acid, which functions as both a catalyst and a dehydrating agent. Via this reaction, formic acid is occasionally employed as a source of CO in the laboratory in lieu of cylinders of this toxic gas. With strong heating, formic acid and some of its derivatives may undergo decarbonylation, even without adding a catalyst. For instance, dimethylformamide slowly decomposes to give dimethylamine and carbon monoxide when heated to its boiling point (154 °C). Som ...
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Metal Carbonyl Complex
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. Metal carbonyls are toxic by skin contact, inhalation or ingestion, in part because of their ability to carbonylate hemoglobin to give carboxyhemoglobin, which prevents the binding of oxygen. Nomenclature and terminology The nomenclature of the metal carbonyls depends on the charge of the complex, the number and type of central atoms, and the number and type of ligands and their binding modes. They occur as neutral complexes, as positively-charged metal carbonyl cations or as negatively charged metal carbonylates. The carbon monoxide ...
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Carbonylation
Carbonylation refers to reactions that introduce carbon monoxide into organic and inorganic substrates. Carbon monoxide is abundantly available and conveniently reactive, so it is widely used as a reactant in industrial chemistry. The term carbonylation also refers to oxidation of protein side chains. Organic chemistry Several industrially useful organic chemicals are prepared by carbonylations, which can be highly selective reactions. Carbonylations produce organic carbonyls, i.e., compounds that contain the C=O functional group such as aldehydes, carboxylic acids and esters. Carbonylations are the basis of many types of reactions, including hydroformylation and Reppe reactions. These reactions require metal catalysts, which bind and activate the CO. These processes involve transition metal acyl complexes as intermediates. Much of this theme was developed by Walter Reppe. Hydroformylation Hydroformylation entails the addition of both carbon monoxide and hydrogen to unsaturated ...
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Photolysis
Photodissociation, photolysis, photodecomposition, or photofragmentation is a chemical reaction in which molecules of a chemical compound are broken down by photons. It is defined as the interaction of one or more photons with one target molecule. Photodissociation is not limited to visible light. Any photon with sufficient energy can affect the chemical bonds of a chemical compound. Since a photon energy, photon's energy is inversely proportional to its wavelength, electromagnetic radiations with the energy of visible light or higher, such as ultraviolet light, x-rays, and gamma rays can induce such reactions. Photolysis in photosynthesis Photolysis is part of the light-dependent reactions, light-dependent reaction or light phase or photochemical phase or Hill reaction of photosynthesis. The general reaction of photosynthetic photolysis can be given in terms of photons as: :\ce + 2 \text \longrightarrow \ce The chemical nature of "A" depends on the type of organism. Purple su ...
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Triruthenium Dodecacarbonyl
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. Structure and synthesis The cluster has ''D3h'' symmetry, consisting of an equilateral triangle of Ru atoms, each of which bears two axial and two equatorial CO ligands. Os3(CO)12 has the same structure, whereas Fe3(CO)12 is different, with two bridging CO ligands, resulting in C2v symmetry. 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. The stoichiometry of the reaction is uncertain, one possibility being the following: :6 RuCl3 + 33 CO + 18 CH3OH → 2 Ru3(CO)12 + 9 CO(OCH3)2 + 18 HCl Reactions The chemical properties of Ru3(CO)12 have been widely studied, and the cluster ...
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Carbon Monoxide
Carbon monoxide (chemical formula CO) is a colorless, poisonous, odorless, tasteless, flammable gas that is slightly less dense than air. Carbon monoxide consists of one carbon atom and one oxygen atom connected by a triple bond. It is the simplest molecule of the oxocarbon family. In coordination complexes the carbon monoxide ligand is called carbonyl. It is a key ingredient in many processes in industrial chemistry. The most common source of carbon monoxide is the partial combustion of carbon-containing compounds, when insufficient oxygen or heat is present to produce carbon dioxide. There are also numerous environmental and biological sources that generate and emit a significant amount of carbon monoxide. It is important in the production of many compounds, including drugs, fragrances, and fuels. Upon emission into the atmosphere, carbon monoxide affects several processes that contribute to climate change. Carbon monoxide has important biological roles across phylogenetic ...
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Osmium Pentacarbonyl
Osmium pentacarbonyl is the organoosmium compound with the formula Os(CO)5. It is the simplest isolatable carbonyl complex of osmium. Osmium pentacarbonyl is a colorless volatile liquid that is obtained by treating solid triosmium dodecacarbonyl under 200 atmospheres of carbon monoxide at 280-290 °C. In contrast, also at 200 atm of CO, solid Ru3(CO)12 converts to Ru(CO)5 at milder temperature of 160 °C. Reactions Samples of Os(CO)5 convert back to the trioosmium cluster upon heating to 80 °C. The analogous conversion of Ru(CO)5 back to Ru3(CO)12 occurs at room temperature. Chlorination Chlorination may refer to: * Chlorination reaction In chemistry, halogenation is a chemical reaction that entails the introduction of one or more halogens into a compound. Halide-containing compounds are pervasive, making this type of transform ... of the pentacarbonyl gives a cationic pentacarbonyl complex: :Os(CO)5 + Cl2 → s(CO)5Clsup>+Cl− Upon UV irradiati ...
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Triosmium Dodecacarbonyl
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. Structure and synthesis The cluster has D3h symmetry, consisting of an equilateral triangle of Os atoms, each of which bears two axial and two equatorial CO ligands. 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 Â (288 pm). Ru3(CO)12 has the same structure, whereas Fe3(CO)12 is different, with two bridging CO ligands resulting in C2v symmetry. Os3(CO)12 is prepared by the direct reaction of OsO4 with carbon monoxide at 175 °C under high pressures: : 3 OsO4 + 24 CO → Os3(CO)12 + 12 CO2 The yield is nearly quantitative. Reactions The chemical properties of O ...
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Organoruthenium Compounds
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. In its organometallic compounds, ruthenium is known to adopt oxidation states from -2 ( u(CO)4sup>2−) to +6 ( uN(Me)4sup>−). Most common are those in the 2+ oxidation state, as illustrated below. File:Grubbs Catalyst 1st Generation.svg, 1st generation Grubbs catalyst File:ShvoCat.png, Shvo catalyst File:RuCymCl2.png, (cymene)ruthenium dichloride dimer File:Trirutheniumdodecacarbonyl.svg, triruthenium dodecacarbonyl. File:Chloro(cyclopentadienyl)bis(triphenylph ...
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