Nitrido Complex
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Nitrido Complex
Metal nitrido complexes are coordination compounds and metal clusters that contain an atom of nitrogen bound only to transition metals. These compounds are ''molecular'', i.e. discrete in contrast to the polymeric, dense nitride materials that are useful in materials science. The distinction between the molecular and solid-state polymers is not always very clear as illustrated by the materials Li6MoN4 and more condensed derivatives such as Na3MoN3. Transition metal nitrido complexes have attracted interest in part because it is assumed that nitrogen fixation proceeds via nitrido intermediates. Nitrido complexes have long been known, the first example being salts of sO3Nsup>−, described in the 19th century. Structural trends Mononuclear complexes feature terminal nitride ligands, typically with short M-N distances consistent with metal ligand multiple bonds. For example, in the anion in PPh4 oNCl4 the Mo-N distance is 163.7 pm. The occurrence of terminal nitrido ligands ...
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Coordination Compound
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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Nitrogen Trichloride
Nitrogen trichloride, also known as trichloramine, is the chemical compound with the formula NCl3. This yellow, oily, pungent-smelling and explosive liquid is most commonly encountered as a byproduct of chemical reactions between ammonia-derivatives and chlorine (for example, in swimming pools). Alongside monochloramine and dichloramine, trichloramine is responsible for the distinctive 'chlorine smell' associated with swimming pools, where the compound is readily formed as a product from hypochlorous acid reacting with ammonia and other nitrogenous substances in the water, such as urea from urine. Preparation and structure The compound is prepared by treatment of ammonium salts, such as ammonium nitrate with chlorine. Intermediates in this conversion include monochloramine and dichloramine, NH2Cl and NHCl2, respectively. Like ammonia, NCl3 is a pyramidal molecule. The N-Cl distances are 1.76 Å, and the Cl-N-Cl angles are 107°. Reactions and uses The chemistry of NCl3 has b ...
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Transition Metal Dinitrogen Complex
Transition metal dinitrogen complexes are coordination compounds that contain transition metals as ion centers the dinitrogen molecules (N2) as ligands. Historical background Transition metal complexes of N2 have been studied since 1965 when the first complex was reported by Allen and Senoff. This diamagnetic complex, 2+.html" ;"title="u(NH3)5(N2)sup>2+">u(NH3)5(N2)sup>2+, was synthesized from hydrazine hydrate and ruthenium trichloride and consists of a u(NH3)5sup>2+ centre attached to one end of N2. The existence of N2 as a ligand in this compound was identified by IR spectrum with a strong band around 2170–2100 cm−1. In 1966, the molecular structure of u(NH3)5(N2)l2 was determined by Bottomly and Nyburg by X-ray crystallography. The dinitrogen complex ''trans''- rCl(N2)(PPh3)2is made by treating Vaska's complex with aromatic acyl azides. It has a planar geometry. The first preparation of a metal-dinitrogen complex using dinitrogen was reported in 1967 by Y ...
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Abiological Nitrogen Fixation
Abiological nitrogen fixation describes chemical processes that fix (react with) N2, usually with the goal of generating ammonia. The dominant technology for abiological nitrogen fixation is the Haber process, which uses an iron-based heterogeneous catalysts and H2 to convert N2 to NH3. This article focuses on homogeneous (soluble) catalysts for the same or similar conversions. Transition metals Vol'pin and Shur An early influential discovery of abiological nitrogen fixation was made by Vol'pin and co-workers in Russia in 1970. Aspects are described in an early review: "using a non-protic Lewis acid, aluminium tribromide, were able to demonstrate the truly catalytic effect of titanium by treating dinitrogen with a mixture of titanium tetrachloride, metallic aluminium, and aluminium tribromide at 50 °C, either in the absence or in the presence of a solvent, e.g. benzene. As much as 200 mol of ammonia per mol of was obtained after hydrolysis.…" These results led ...
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Interstitial Compound
In materials science, an interstitial defect is a type of point crystallographic defect where an atom of the same or of a different type, occupies an interstitial site in the crystal structure. When the atom is of the same type as those already present they are known as a self-interstitial defect. Alternatively, small atoms in some crystals may occupy interstitial sites, such as hydrogen in palladium. Interstitials can be produced by bombarding a crystal with elementary particles having energy above the displacement threshold for that crystal, but they may also exist in small concentrations in thermodynamic equilibrium. The presence of interstitial defects can modify the physical and chemical properties of a material. History The idea of interstitial compounds was started in the late 1930s and they are often called Hagg phases after Hägg. Transition metals generally crystallise in either the hexagonal close packed or face centered cubic structures, both of which can be consider ...
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Bridging Ligand
In coordination chemistry, a bridging ligand is a ligand that connects two or more atoms, usually metal ions. The ligand may be atomic or polyatomic. Virtually all complex organic compounds can serve as bridging ligands, so the term is usually restricted to small ligands such as pseudohalides or to ligands that are specifically designed to link two metals. In naming a complex wherein a single atom bridges two metals, the bridging ligand is preceded by the Greek letter mu, μ, with a subscript number denoting the number of metals bound to the bridging ligand. μ2 is often denoted simply as μ. When describing coordination complexes care should be taken not to confuse μ with η ('eta'), which relates to hapticity. Ligands that are not bridging are called terminal ligands. List of bridging ligands Virtually all ligands are known to bridge, with the exception of amines and ammonia. Common bridging ligands include most of the common anions. Many simple organic ligands form str ...
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Phosphine
Phosphine (IUPAC name: phosphane) is a colorless, flammable, highly toxic compound with the chemical formula , classed as a pnictogen hydride. Pure phosphine is odorless, but technical grade samples have a highly unpleasant odor like rotting fish, due to the presence of substituted phosphine and diphosphane (). With traces of present, is spontaneously flammable in air ( pyrophoric), burning with a luminous flame. Phosphine is a highly toxic respiratory poison, and is immediately dangerous to life or health at 50 ppm. Phosphine has a trigonal pyramidal structure. Phosphines are compounds that include and the organophosphines, which are derived from by substituting one or more hydrogen atoms with organic groups. They have the general formula . Phosphanes are saturated phosphorus hydrides of the form , such as triphosphane. Phosphine, PH3, is the smallest of the phosphines and the smallest of the phosphanes. History Philippe Gengembre (1764–1838), a student of Lavois ...
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Alkylation
Alkylation is the transfer of an alkyl group from one molecule to another. The alkyl group may be transferred as an alkyl carbocation, a free radical, a carbanion, or a carbene (or their equivalents). Alkylating agents are reagents for effecting alkylation. Alkyl groups can also be removed in a process known as dealkylation. Alkylating agents are often classified according to their nucleophilic or electrophilic character. In oil refining contexts, alkylation refers to a particular alkylation of isobutane with olefins. For upgrading of petroleum, alkylation produces a premium blending stock for gasoline. In medicine, alkylation of DNA is used in chemotherapy to damage the DNA of cancer cells. Alkylation is accomplished with the class of drugs called alkylating antineoplastic agents. Nucleophilic alkylating agents Nucleophilic alkylating agents deliver the equivalent of an alkyl anion ( carbanion). The formal "alkyl anion" attacks an electrophile, forming a new covalent ...
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Protonation
In chemistry, protonation (or hydronation) is the adding of a proton (or hydron, or hydrogen cation), (H+) to an atom, molecule, or ion, forming a conjugate acid. (The complementary process, when a proton is removed from a Brønsted–Lowry acid, is deprotonation.) Some examples include *The protonation of water by sulfuric acid: *:H2SO4 + H2O H3O+ + *The protonation of isobutene in the formation of a carbocation: *:(CH3)2C=CH2 + HBF4 (CH3)3C+ + *The protonation of ammonia in the formation of ammonium chloride from ammonia and hydrogen chloride: *:NH3( g) + HCl( g) → NH4Cl( s) Protonation is a fundamental chemical reaction and is a step in many stoichiometric and catalytic processes. Some ions and molecules can undergo more than one protonation and are labeled polybasic, which is true of many biological macromolecules. Protonation and deprotonation (removal of a proton) occur in most acid–base reactions; they are the core of most acid–base reaction theories. A Brønst ...
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Nitrile
In organic chemistry, a nitrile is any organic compound that has a functional group. The prefix ''cyano-'' is used interchangeably with the term ''nitrile'' in industrial literature. Nitriles are found in many useful compounds, including methyl cyanoacrylate, used in super glue, and nitrile rubber, a nitrile-containing polymer used in latex-free laboratory and medical gloves. Nitrile rubber is also widely used as automotive and other seals since it is resistant to fuels and oils. Organic compounds containing multiple nitrile groups are known as cyanocarbons. Inorganic compounds containing the group are not called nitriles, but cyanides instead. Though both nitriles and cyanides can be derived from cyanide salts, most nitriles are not nearly as toxic. Structure and basic properties The N−C−C geometry is linear in nitriles, reflecting the sp hybridization of the triply bonded carbon. The C−N distance is short at 1.16  Å, consistent with a triple bond. Nitriles a ...
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Transition Metal Azide Complex
Transition metal azide complexes are coordination complexes containing one or more azide (N3−) ligands. Structure and bonding Azide is a pseudohalide but more nucleophilic than chloride. As a monodentate ligand, azide binds through one of the two terminal nitrogen atoms, i.e. M-N=N=N. The N3 unit is linear or nearly so. The M-N-N angles are quite bent. Azide functions as a bridging ligand via two bonding modes. Commonly the metals share the same nitrogen ("N-diazonium" mode). Less common is the motif M-N=N=N-M, illustrated by u(N3)(PPh3)2sub>2. Homoleptic complexes Many homoleptic complexes (with only one kind of ligand) are known. Coordination numbers range from 2 (e.g., u(N3)2sup>−) to 7 (e.g., (N3)7sup>−). Many homoleptic complexes are octahedral anions of the type (N3)6sup>n-: *dianions for tetravalent metals V, Pt, Ti, Zr, Hf *trianions for trivalent metals Cr, Fe, Ru, Rh, Ir *tetraanions for the divalent Ni For some metals, homoleptic complexes exist in two ...
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