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Template Reaction
In coordination chemistry, a template reaction is any of a class of ligand-based reactions that occur between two or more adjacent coordination sites on a metal center. In the absence of the metal ion, the same organic reactants produce different products. The template effects emphasizes the pre-organization provided by the coordination sphere, although the coordination modifies the electronic properties (acidity, electrophilicity, etc.) of ligands. An early example is the dialkylation of a nickel dithiolate: : The corresponding alkylation in the absence of a metal ion would yield polymers. Crown ethers arise from dialkylations that are templated by alkali metals. Other template reactions include the Mannich and Schiff base condensations. The condensation of formaldehyde, ammonia, and tris(ethylenediamine)cobalt(III) to give a clathrochelate complex is one example. The phosphorus analogue of an aza crown can be prepared by a template reaction. Where it is not possible to ...
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Coordination Chemistry
A coordination complex consists of a central atom or ion, which is usually metallic and is called the ''coordination centre'', and a surrounding array of bound molecules or ions, that are in turn known as ''ligands'' or complexing agents. Many metal-containing compounds, especially those that include transition metals (elements like titanium that belong to the Periodic Table's d-block), are coordination complexes. Nomenclature and terminology Coordination complexes are so pervasive that their structures and reactions are described in many ways, sometimes confusingly. The atom within a ligand that is bonded to the central metal atom or ion is called the donor atom. In a typical complex, a metal ion is bonded to several donor atoms, which can be the same or different. A polydentate (multiple bonded) ligand is a molecule or ion that bonds to the central atom through several of the ligand's atoms; ligands with 2, 3, 4 or even 6 bonds to the central atom are common. These compl ...
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Tris(ethylenediamine)cobalt(III)
Tris(ethylenediamine)cobalt(III) chloride is an inorganic compound with the formula o(en)3l3 (where "en" is the abbreviation for ethylenediamine). It is the chloride salt of the coordination complex o(en)3sup>3+. This trication was important in the history of coordination chemistry because of its stability and its stereochemistry. Many different salts have been described. The complex was first described by Alfred Werner who isolated this salt as yellow-gold needle-like crystals. Synthesis and structure The compound is prepared from an aqueous solution of ethylenediamine and virtually any cobalt(II) salt, such as cobalt(II) chloride. The solution is purged with air to oxidize the cobalt(II)-ethylenediamine complexes to cobalt(III). The reaction proceeds in 95% yield, and the trication can be isolated with a variety of anions. A detailed product analysis of a large-scale synthesis revealed that one minor by-product was o(en)2Cl(H2NCH2CH2NH3)l3, which contains a rare monoden ...
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Homogeneous Catalysis
In chemistry, homogeneous catalysis is catalysis by a soluble catalyst in a solution. Homogeneous catalysis refers to reactions where the catalyst is in the same phase as the reactants, principally in solution. In contrast, heterogeneous catalysis describes processes where the catalysts and substrate are in distinct phases, typically solid-gas, respectively. The term is used almost exclusively to describe solutions and implies catalysis by organometallic compounds. Homogeneous catalysis is an established technology that continues to evolve. An illustrative major application is the production of acetic acid. Enzymes are examples of homogeneous catalysts. Examples Acid catalysis The proton is a pervasive homogeneous catalyst because water is the most common solvent. Water forms protons by the process of self-ionization of water. In an illustrative case, acids accelerate (catalyze) the hydrolysis of esters: :CH3CO2CH3 + H2O CH3CO2H + CH3OH At neutral pH, aqueous solutions of most e ...
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Catalysis
Catalysis () is the process of increasing the rate of a chemical reaction by adding a substance known as a catalyst (). Catalysts are not consumed in the reaction and remain unchanged after it. If the reaction is rapid and the catalyst recycles quickly, very small amounts of catalyst often suffice; mixing, surface area, and temperature are important factors in reaction rate. Catalysts generally react with one or more reactants to form intermediates that subsequently give the final reaction product, in the process of regenerating the catalyst. Catalysis may be classified as either homogeneous, whose components are dispersed in the same phase (usually gaseous or liquid) as the reactant, or heterogeneous, whose components are not in the same phase. Enzymes and other biocatalysts are often considered as a third category. Catalysis is ubiquitous in chemical industry of all kinds. Estimates are that 90% of all commercially produced chemical products involve catalysts at some s ...
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Porphyrin
Porphyrins ( ) are a group of heterocyclic macrocycle organic compounds, composed of four modified pyrrole subunits interconnected at their α carbon atoms via methine bridges (=CH−). The parent of porphyrin is porphine, a rare chemical compound of exclusively theoretical interest. Substituted porphines are called porphyrins. With a total of 26 π-electrons, of which 18 π-electrons form a planar, continuous cycle, the porphyrin ring structure is often described as aromatic. One result of the large conjugated system is that porphyrins typically absorb strongly in the visible region of the electromagnetic spectrum, i.e. they are deeply colored. The name "porphyrin" derives from the Greek word πορφύρα (''porphyra''), meaning ''purple''. Complexes of porphyrins Concomitant with the displacement of two N-''H'' protons, porphyrins bind metal ions in the N4 "pocket". The metal ion usually has a charge of 2+ or 3+. A schematic equation for these syntheses is shown: :H2porp ...
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Phthalonitrile
Phthalonitrile is an organic compound with the formula C6H4(CN)2, which is an off-white crystal solid at room temperature. It is a derivative of benzene, containing two adjacent nitrile groups. The compound has low solubility in water but is soluble in common organic solvents. The compound is used as a precursor to phthalocyanine and other pigments, fluorescent brighteners, and photographic sensitizers. Synthesis Phthalonitrile is produced industrially in a single-stage continuous process, by the ammoxidation of ''o''-xylene at 480 °C. The reaction is catalyzed by vanadium oxide-antimony-oxide in a fluidized bed reactor.Lorz, Peter M. "Phthalic Acid and Derivatives" in Ulmanns Encyclopedia of Industrial Chemistry. Wiley-VCH: Weinheim, 2002. . : Phthalonitrile was first described in 1896 by Johannes Pinnow. It was noted as a byproduct of the synthesis of ortho-dicyanodiazoamidobenzene via the reaction of ortho-amidobenzonitrile hydrochloride, sodium nitrite, and hydroc ...
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Phthalocyanine
Phthalocyanine () is a large, aromatic, macrocyclic, organic compound with the formula and is of theoretical or specialized interest in chemical dyes and photoelectricity. It is composed of four isoindole units linked by a ring of nitrogen atoms. = has a two-dimensional geometry and a ring system consisting of 18  π-electrons. The extensive delocalization of the π-electrons affords the molecule useful properties, lending itself to applications in dyes and pigments. Metal complexes derived from , the conjugate base of , are valuable in catalysis, organic solar cells, and photodynamic therapy. Properties Phthalocyanine and derived metal complexes (MPc) tend to aggregate and, thus, have low solubility in common solvents. Benzene at 40 °C dissolves less than a milligram of or CuPc per litre. and CuPc dissolve easily in sulfuric acid due to the protonation of the nitrogen atoms bridging the pyrrole rings. Many phthalocyanine compounds are, thermally, very stabl ...
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Decomplexation
In chemistry, decomplexation refers to the removal of a ligand from a coordination complex. Decomplexation is of particular interest when the ligand has been synthesized within the coordination sphere of the metal, as is often the case in organometallic chemistry. Decomplexation by ligand displacement Ligands can be decomplexed by displacement with another ligand, e.g., a highly basic ligand or the use of high pressures of carbon monoxide. Arenes are liberated from (arene)Cr(CO)3 with pyridine: :(arene)Cr(CO)3 + 3 C5H5N → Cr(CO)3(NC5H5)3 + arene In this case Cr(CO)3(pyridine)3 can be recycled. Illustrative of this approach is the synthesis of (–)-steganone via a chromium haloarene complex. The synthesis is completed by decomplexation, liberating the natural product. ''(16)'' 1,4,7-Trithiacyclononane can be prepared within the coordination sphere of a metal, and then isolated by decomplexation. : Oxidative decomplexation Another popular method for decomplexation ...
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Journal Of The American Chemical Society
The ''Journal of the American Chemical Society'' is a weekly peer-reviewed scientific journal that was established in 1879 by the American Chemical Society. The journal has absorbed two other publications in its history, the ''Journal of Analytical and Applied Chemistry'' (July 1893) and the ''American Chemical Journal'' (January 1914). It covers all fields of chemistry. Since 2021, the editor-in-chief is Erick M. Carreira (ETH Zurich). In 2014, the journal moved to a hybrid open access publishing model. Abstracting and indexing The journal is abstracted and indexed in Chemical Abstracts Service, Scopus, EBSCO databases, ProQuest databases, Index Medicus/MEDLINE/PubMed, and the Science Citation Index Expanded. According to the ''Journal Citation Reports'', the journal has a 2021 impact factor of 16.383. Editors-in-chief The following people are or have been editor-in-chief: * 1879–1880 – Hermann Endemann * 1880–1881 – Gideon E. Moore * 1881–1882 – Hermann Endemann ...
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Aza Crown
In organic chemistry, an aza-crown ether is an aza analogue of a crown ether (cyclic polyether). That is, it has a nitrogen atom (amine linkage, or ) in place of each oxygen atom (ether linkage, ) around the ring. While the parent crown ethers have the formulae , the parent ''aza''-crown ethers have the formulae , where n = 3, 4, 5, 6. Well-studied aza crowns include triazacyclononane (n = 3), cyclen (n = 4), and hexaaza-18-crown-6 (n = 6). File:Me3TACN.png, 1,4,7-Trimethyl-1,4,7-triazacyclononane, a tridentate ligand used in coordination chemistry. File:Cyclam.png, Cyclam is a tetraaza crown ether with alternating and linkers between amine centers. File:Plerixafor.svg, Plerixafor, a derivative of cyclam, is used to treat lymphoma and multiple myeloma. File:Cryptand.svg, 2.2.2-Cryptand is an aza-crown of the mixed ether-amine variety. Synthesis The synthesis of aza crown ethers are subject to the challenges associated with the preparation of macrocycles. The 18-membered r ...
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