Nitrosyl Complexes
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Nitrosyl Complexes
In organic chemistry, nitroso refers to a functional group in which the nitric oxide () group is attached to an organic moiety (chemistry), moiety. As such, various nitroso groups can be categorized as ''C''-nitroso compounds (e.g., nitrosoalkanes; ), ''S''-nitroso compounds (S-Nitrosothiol, nitrosothiols; ), ''N''-nitroso compounds (e.g., nitrosamines, ), and ''O''-nitroso compounds (alkyl nitrites; ). Synthesis Nitroso compounds can be prepared by the reduction of nitro compounds or by the oxidation of hydroxylamines. Ortho-nitrosophenols may be produced by the Baudisch reaction. In the Fischer–Hepp rearrangement, aromatic 4-nitrosoanilines are prepared from the corresponding nitrosamines. Properties Nitrosoarenes typically participate in a Dimerization (chemistry), monomer–dimer equilibrium. The azobenzene ''N'',''N'-''dioxide (Ar(–O)N+=+N(O–)Ar) dimers, which are often pale yellow, are generally favored in the solid state, whereas the deep-green monomers are fav ...
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Cambridge University Press
Cambridge University Press was the university press of the University of Cambridge. Granted a letters patent by King Henry VIII in 1534, it was the oldest university press in the world. Cambridge University Press merged with Cambridge Assessment to form Cambridge University Press and Assessment under Queen Elizabeth II's approval in August 2021. With a global sales presence, publishing hubs, and offices in more than 40 countries, it published over 50,000 titles by authors from over 100 countries. Its publications include more than 420 academic journals, monographs, reference works, school and university textbooks, and English language teaching and learning publications. It also published Bibles, runs a bookshop in Cambridge, sells through Amazon, and has a conference venues business in Cambridge at the Pitt Building and the Sir Geoffrey Cass Sports and Social Centre. It also served as the King's Printer. Cambridge University Press, as part of the University of Cambridge, was a ...
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Barton Reaction
The Barton reaction, also known as the Barton nitrite ester reaction, is a photochemical reaction that involves the photolysis of an alkyl nitrite to form a δ-nitroso Alcohol (chemistry), alcohol. Discovered in 1960, the reaction is named for its discoverer, Nobel laureate Sir Derek Barton. Barton's Nobel Prize in Chemistry in 1969 was awarded for his work on understanding conformations of organic molecules, work which was key to realizing the utility of the Barton Reaction. The Barton reaction involves a homolysis (chemistry), homolytic RO–NO cleavage, followed by δ-hydrogen abstraction, free radical recombination, and tautomerization to form an oxime. Selectivity for the δ-hydrogen is a result of the conformation of the 6-membered radical intermediate. Often, the site of hydrogen atom abstraction can be easily predicted. This allows the regio- and stereo-selective introduction of functionality into complicated molecules with high yield. Due to its unique property at the time ...
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Transition Metal Nitroso Complexes
Structure of the dye Naphthol Green B, which features of nitroso ligand bound to Fe(III). Transition metal nitroso complexes are coordination complexes containing one or more organonitroso ligands (RNO). Structure and bonding Organic nitroso compounds bind to metals in several ways, but most commonly as monodentate N-bonded ligands. Also known are O-bonded, η2-N,O-bonded. Dimers of organic nitroso compounds also bind in a κ2--O,O bidentate manner. Illustrative are , where a pair nitrosobenzenes are monodentate, and where two nitrosobenzenes bridge. Chelating nitroso ligands : Arylnitroso compounds with a flanking hydroxy group are a well-developed, e.g. 1-nitroso-2-naphthol. They are precursors to anionic N,O chelating ligands. Chelating dinitrosoarenes are uncommon but have been investigated. Synthesis Organic nitroso complexes can be prepared from preformed organic nitroso precursors. These precursors usually exist as N-N bonded dimers, but the dimer dissociates read ...
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Ligand
In coordination chemistry, a ligand is an ion or molecule with a functional group that binds to a central metal atom to form a coordination complex. The bonding with the metal generally involves formal donation of one or more of the ligand's electron pairs, often through Lewis acids and bases, Lewis bases. The nature of metal–ligand bonding can range from covalent bond, covalent to ionic bond, ionic. Furthermore, the metal–ligand bond order can range from one to three. Ligands are viewed as Lewis bases, although rare cases are known to involve Lewis acids and bases, Lewis acidic "ligands". Metals and metalloids are bound to ligands in almost all circumstances, although gaseous "naked" metal ions can be generated in a high vacuum. Ligands in a complex dictate the reactivity (chemistry), reactivity of the central atom, including ligand substitution rates, the reactivity of the ligands themselves, and redox. Ligand selection requires critical consideration in many practical are ...
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Bond Dissociation Energy
The bond-dissociation energy (BDE, ''D''0, or ''DH°'') is one measure of the strength of a chemical bond . It can be defined as the standard enthalpy change when is cleaved by homolysis to give fragments A and B, which are usually radical species. The enthalpy change is temperature-dependent, and the bond-dissociation energy is often defined to be the enthalpy change of the homolysis at 0  K (absolute zero), although the enthalpy change at 298 K ( standard conditions) is also a frequently encountered parameter. As a typical example, the bond-dissociation energy for one of the C−H bonds in ethane () is defined as the standard enthalpy change of the process : , : ''DH''°298() = Δ''H°'' = 101.1(4) kcal/mol = 423.0 ± 1.7 kJ/mol = 4.40(2)  eV (per bond). To convert a molar BDE to the energy needed to dissociate the bond ''per molecule'', the conversion factor 23.060 kcal/mol (96.485 kJ/mol) for each eV can be used. A variety of experi ...
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Free Radical
A daughter category of ''Ageing'', this category deals only with the biological aspects of ageing. Ageing Biogerontology Biological processes Causes of death Cellular processes Gerontology Life extension Metabolic disorders Metabolism Old age Time in life {{CatAutoTOC ...
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Quinone
The quinones are a class of organic compounds that are formally "derived from aromatic compounds benzene.html" ;"title="uch as benzene">uch as benzene or naphthalene] by conversion of an even number of –CH= groups into –C(=O)– groups with any necessary rearrangement of double bonds", resulting in "a fully Conjugated system, conjugated cyclic diketone, dione structure". The archetypical member of the class is 1,4-benzoquinone or cyclohexadienedione, often called simply "quinone" (thus the name of the class). Other important examples are 1,2-benzoquinone (''ortho''-quinone), 1,4-naphthoquinone and 9,10-anthraquinone. The name is derived from that of quinic acid (with the suffix "-one" indicating a ketone), since it is one of the compounds obtained upon oxidation of quinic acid. Quinic acid, like quinine is obtained from cinchona bark, called quinaquina in the indigenous languages of Peruvian tribes. Properties Quinones are oxidized derivatives of aromatic compounds an ...
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Oxime
In organic chemistry, an oxime is an organic compound belonging to the imines, with the general Chemical formula, formula , where R is an organic Side chain, side-chain and R' may be hydrogen, forming an aldoxime, or another organic functional group, group, forming a ketoxime. O-substituted oximes form a closely related family of compounds. Amidoximes are oximes of amides () with general structure . Oximes are usually generated by the reaction of hydroxylamine with aldehydes () or ketones (). The term ''oxime'' dates back to the 19th century, a combination of the words ''oxygen'' and ''imine''. Structure and properties If the two side-chains on the central carbon are different from each other—either an aldoxime, or a ketoxime with two different "R" groups—the oxime can often have two different geometric stereoisomeric forms according to the E/Z configuration, ''E''/''Z'' configuration. An older terminology of Descriptor (chemistry)#syn, anti, ''syn'' and ''anti'' was used to ...
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Rearrangement Reaction
In organic chemistry, a rearrangement reaction is a broad class of organic reactions where the carbon skeleton of a molecule is rearranged to give a structural isomer of the original molecule. Often a substituent moves from one atom to another atom in the same molecule, hence these reactions are usually intramolecular. In the example below, the substituent R moves from carbon atom 1 to carbon atom 2: :\underset\ce\ce\underset\ce\ce Intermolecular rearrangements also take place. A rearrangement is not well represented by simple and discrete electron transfers (represented by curved arrows in organic chemistry texts). The actual mechanism of alkyl groups moving, as in Wagner–Meerwein rearrangement, probably involves transfer of the moving alkyl group fluidly along a bond, not ionic bond-breaking and forming. In pericyclic reactions, explanation by orbital interactions give a better picture than simple discrete electron transfers. It is, nevertheless, possible to draw the curved ...
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