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Shilov System
The Shilov system is a classic example of catalytic C-H bond activation and oxidation which preferentially activates stronger C-H bonds over weaker C-H bonds for an overall partial oxidation. C. I. Herrerias, X. Yao, Z. Li, C.-J. Li, Reactions of C-H Bonds in Water, ''Chem. Rev.''; 2007; 107(6); 2546-2562. Overview The Shilov system was discovered by Alexander E. Shilov in 1969-1972 while investigating H/D exchange between isotopologues of CH4 and H2O catalyzed simple transition metal coordination complexes. The Shilov cycle is the partial oxidation of a hydrocarbon to an alcohol or alcohol precursor (RCl) catalyzed by PtIICl2 in an aqueous solution with 2−.html" ;"title="tIVCl6sup>2−">tIVCl6sup>2− acting as the ultimate oxidant. The cycle consists of three major steps, the electrophilic activation of the C-H bond, oxidation of the complex, and the nucleophilic oxidation of the alkane substrate. An equivalent transformation is performed industrially by steam refor ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Shilov Cycle
The Shilov system is a classic example of catalytic C-H bond activation and oxidation which preferentially activates stronger C-H bonds over weaker C-H bonds for an overall partial oxidation. C. I. Herrerias, X. Yao, Z. Li, C.-J. Li, Reactions of C-H Bonds in Water, ''Chem. Rev.''; 2007; 107(6); 2546-2562. Overview The Shilov system was discovered by Alexander E. Shilov in 1969-1972 while investigating H/D exchange between isotopologues of CH4 and H2O catalyzed simple transition metal coordination complexes. The Shilov cycle is the partial oxidation of a hydrocarbon to an alcohol or alcohol precursor (RCl) catalyzed by PtIICl2 in an aqueous solution with 2−.html" ;"title="tIVCl6sup>2−">tIVCl6sup>2− acting as the ultimate oxidant. The cycle consists of three major steps, the electrophilic activation of the C-H bond, oxidation of the complex, and the nucleophilic oxidation of the alkane substrate. An equivalent transformation is performed industrially by steam refor ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Alkane
In organic chemistry, an alkane, or paraffin (a historical trivial name that also has other meanings), is an acyclic saturated hydrocarbon. In other words, an alkane consists of hydrogen and carbon atoms arranged in a tree structure in which all the carbon–carbon bonds are single. Alkanes have the general chemical formula . The alkanes range in complexity from the simplest case of methane (), where ''n'' = 1 (sometimes called the parent molecule), to arbitrarily large and complex molecules, like pentacontane () or 6-ethyl-2-methyl-5-(1-methylethyl) octane, an isomer of tetradecane (). The International Union of Pure and Applied Chemistry (IUPAC) defines alkanes as "acyclic branched or unbranched hydrocarbons having the general formula , and therefore consisting entirely of hydrogen atoms and saturated carbon atoms". However, some sources use the term to denote ''any'' saturated hydrocarbon, including those that are either monocyclic (i.e. the cycloalkanes) or ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Carbon Dioxide
Carbon dioxide (chemical formula ) is a chemical compound made up of molecules that each have one carbon atom covalently double bonded to two oxygen atoms. It is found in the gas state at room temperature. In the air, carbon dioxide is transparent to visible light but absorbs infrared radiation, acting as a greenhouse gas. It is a trace gas in Earth's atmosphere at 421 parts per million (ppm), or about 0.04% by volume (as of May 2022), having risen from pre-industrial levels of 280 ppm. Burning fossil fuels is the primary cause of these increased CO2 concentrations and also the primary cause of climate change.IPCC (2022Summary for policy makersiClimate Change 2022: Mitigation of Climate Change. Contribution of Working Group III to the Sixth Assessment Report of the Intergovernmental Panel on Climate Change Cambridge University Press, Cambridge, United Kingdom and New York, NY, USA Carbon dioxide is soluble in water and is found in groundwater, lakes, ice caps, ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Water
Water (chemical formula ) is an inorganic, transparent, tasteless, odorless, and nearly colorless chemical substance, which is the main constituent of Earth's hydrosphere and the fluids of all known living organisms (in which it acts as a solvent). It is vital for all known forms of life, despite not providing food, energy or organic micronutrients. Its chemical formula, H2O, indicates that each of its molecules contains one oxygen and two hydrogen atoms, connected by covalent bonds. The hydrogen atoms are attached to the oxygen atom at an angle of 104.45°. "Water" is also the name of the liquid state of H2O at standard temperature and pressure. A number of natural states of water exist. It forms precipitation in the form of rain and aerosols in the form of fog. Clouds consist of suspended droplets of water and ice, its solid state. When finely divided, crystalline ice may precipitate in the form of snow. The gaseous state of water is steam or water vapor. Water co ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Sigma-bond Metathesis
In organometallic chemistry, sigma-bond metathesis is a chemical reaction wherein a metal-ligand sigma bond undergoes metathesis (exchange of parts) with the sigma bond in some reagent. The reaction is illustrated by the exchange of lutetium(III) methyl complex with a hydrocarbon (R-H): :(C5Me5)2Lu-CH3 + R-H → (C5Me5)2Lu-R + CH4 This reactivity was first observed by Patricia Watson, a researcher at duPont.{{cite journal, author=Watson, Patricia, title=Methane exchange reactions of lanthanide and early-transition-metal methyl complexes, journal=Journal of the American Chemical Society, year=1983, volume=32, pages=6491–6493, doi=10.1021/ja00359a023 The reaction is mainly observed for complexes of metals with d0 configuration, e.g. complexes of Sc(III), Zr(IV), Nb(IV), Ta(V), etc. f-Element complexes also participate, regardless of the number of f-electrons. The reaction is thought to proceed via cycloaddition. Indeed, the rate of the reaction is characterized by a highly ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Oxidative Addition
Oxidative addition and reductive elimination are two important and related classes of reactions in organometallic chemistry. Oxidative addition is a process that increases both the oxidation state and coordination number of a metal centre. Oxidative addition is often a step in catalytic cycles, in conjunction with its reverse reaction, reductive elimination. Role in transition metal chemistry For transition metals, oxidative reaction results in the decrease in the d''n'' to a configuration with fewer electrons, often 2e fewer. Oxidative addition is favored for metals that are (i) basic and/or (ii) easily oxidized. Metals with a relatively low oxidation state often satisfy one of these requirements, but even high oxidation state metals undergo oxidative addition, as illustrated by the oxidation of Pt(II) with chlorine: : tCl4sup>2− + Cl2 → tCl6sup>2− In classical organometallic chemistry, the formal oxidation state of the metal and the electron count of the complex both in ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Methane Monooxygenase
Methane monooxygenase (MMO) is an enzyme capable of oxidizing the C-H bond in methane as well as other alkanes. Methane monooxygenase belongs to the class of oxidoreductase enzymes (). There are two forms of MMO: the well-studied soluble form (sMMO) and the particulate form (pMMO). The active site in sMMO contains a di-iron center bridged by an oxygen atom (Fe-O-Fe), whereas the active site in pMMO utilizes copper. Structures of both proteins have been determined by X-ray crystallography; however, the location and mechanism of the active site in pMMO is still poorly understood and is an area of active research. The particulate methane monooxygenase and related ammonia monooxygenase are integral membrane proteins, occurring in methanotrophs and ammonia oxidisers, respectively, which are thought to be related. These enzymes have a relatively wide substrate specificity and can catalyse the oxidation of a range of substrates including ammonia, methane, halogenated hydrocarbons, and ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Methanol
Methanol (also called methyl alcohol and wood spirit, amongst other names) is an organic chemical and the simplest aliphatic alcohol, with the formula C H3 O H (a methyl group linked to a hydroxyl group, often abbreviated as MeOH). It is a light, volatile, colourless, flammable liquid with a distinctive alcoholic odour similar to that of ethanol (potable alcohol). A polar solvent, methanol acquired the name wood alcohol because it was once produced chiefly by the destructive distillation of wood. Today, methanol is mainly produced industrially by hydrogenation of carbon monoxide. Methanol consists of a methyl group linked to a polar hydroxyl group. With more than 20 million tons produced annually, it is used as a precursor to other commodity chemicals, including formaldehyde, acetic acid, methyl tert-butyl ether, methyl benzoate, anisole, peroxyacids, as well as a host of more specialised chemicals. Occurrence Small amounts of methanol are present in normal, healthy hu ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
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 ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Syngas
Syngas, or synthesis gas, is a mixture of hydrogen and carbon monoxide, in various ratios. The gas often contains some carbon dioxide and methane. It is principly used for producing ammonia or methanol. Syngas is combustible and can be used as a fuel. Historically, it has been used as a replacement for gasoline, when gasoline supply has been limited; for example, wood gas was used to power cars in Europe during WWII (in Germany alone half a million cars were built or rebuilt to run on wood gas). Production Syngas is produced by steam reforming or partial oxidation of natural gas or liquid hydrocarbons, or coal gasification. Steam reforming of methane is an endothermic reaction requiring 206 kJ/mol of methane: : In principle, but rarely in practice, biomass and related hydrocarbon feedstocks could be used to generate biogas and biochar in waste-to-energy gasification facilities. The gas generated (mostly methane and carbon dioxide) is sometimes described as ''syngas'' but its co ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Steam Reforming
Steam reforming or steam methane reforming (SMR) is a method for producing syngas (hydrogen and carbon monoxide) by reaction of hydrocarbons with water. Commonly natural gas is the feedstock. The main purpose of this technology is hydrogen production. The reaction is represented by this equilibrium: :CH4 + H2O CO + 3 H2 The reaction is strongly endothermic (Δ''H''SR = 206 kJ/mol). Hydrogen produced by steam reforming is termed 'grey hydrogen' when the waste carbon monoxide is released to the atmosphere and 'blue hydrogen' when the carbon monoxide is (mostly) captured and stored geologically - see carbon capture and storage. Zero carbon 'green' hydrogen is produced by thermochemical water splitting, using solar thermal, low- or zero-carbon electricity or waste heat, or electrolysis, using low- or zero-carbon electricity. Zero carbon emissions 'turquoise' hydrogen is produced by one-step methane pyrolysis of natural gas. Steam reforming of natural gas produces most of the world ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Nucleophilic
In chemistry, a nucleophile is a chemical species that forms bonds by donating an electron pair. All molecules and ions with a free pair of electrons or at least one pi bond can act as nucleophiles. Because nucleophiles donate electrons, they are Lewis bases. ''Nucleophilic'' describes the affinity of a nucleophile to bond with positively charged atomic nuclei. Nucleophilicity, sometimes referred to as nucleophile strength, refers to a substance's nucleophilic character and is often used to compare the affinity of atoms. Neutral nucleophilic reactions with solvents such as alcohols and water are named solvolysis. Nucleophiles may take part in nucleophilic substitution, whereby a nucleophile becomes attracted to a full or partial positive charge, and nucleophilic addition. Nucleophilicity is closely related to basicity. History The terms ''nucleophile'' and ''electrophile'' were introduced by Christopher Kelk Ingold in 1933, replacing the terms ''anionoid'' and ''cationoid' ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
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