Coordination Environment
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Coordination Environment
In coordination chemistry, the first coordination sphere refers to the array of molecules and ions (the ligands) directly attached to the central metal atom. The second coordination sphere consists of molecules and ions that attached in various ways to the first coordination sphere. First coordination sphere The first coordination sphere refers to the molecules that are attached directly to the metal. The interactions between the first and second coordination spheres usually involve hydrogen-bonding. For charged complexes, ion pairing is important. In hexamminecobalt(III) chloride ( o(NH3)6l3), the cobalt cation plus the 6 ammonia ligands comprise the first coordination sphere. The coordination sphere of this ion thus consists of a central MN6 core "decorated" by 18 N−H bonds that radiate outwards. Second coordination sphere Metal ions can be described as consisting of series of two concentric coordination spheres, the first and second. More distant from the second coor ...
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MP2N2M&P2NM
MP, Mp, mp, or .mp may refer to: Arts and entertainment * ''M.P.'' (opera), an 1811 comic opera by Thomas Moore and Charles Edward Horn * Magic point, or mana point, in role-playing games * (''mp''), a musical dynamic meaning "medium-quiet" or "moderately-quiet" * Multiplayer, in gaming * Multipremier, a Mexican television network * , whose station identification is "mp" * ''Mario Party'', a series of party vídeo games produced by Nintendo * MP signature on works by Australian artist Margaret Preston * Mike Portnoy, drummer of the progressive metal band Dream Theater Businesses and organizations Government * Member of Parliament * Ministry of Planning, Budget, and Management (Brazil), a cabinet-level federal ministry in Brazil * Public Ministry (Portugal) (), the body of the Judiciary of Portugal * Public Prosecutor's Office (Brazil) (), the Brazilian body of independent public prosecutors Police * Military police, law enforcement agencies connected with, or part of, the m ...
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Ligand Cone Angle
In coordination chemistry, the ligand cone angle (θ) is a measure of the steric bulk of a ligand in a transition metal coordination complex. It is defined as the solid angle formed with the metal at the vertex of a cone and the outermost edge of the van der Waals spheres of the ligand atoms at the perimeter of the base of the cone. Tertiary phosphine ligands are commonly classified using this parameter, but the method can be applied to any ligand. The term ''cone angle'' was first introduced by Chadwick A. Tolman, a research chemist at DuPont. Tolman originally developed the method for phosphine ligands in nickel complexes, determining them from measurements of accurate physical models. Asymmetric cases The concept of cone angle is most easily visualized with symmetrical ligands, e.g. PR3. But the approach has been refined to include less symmetrical ligands of the type PRR′R″ as well as diphosphines. In such asymmetric cases, the substituent angles' half angles, , are ...
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Coordination Number
In chemistry, crystallography, and materials science, the coordination number, also called ligancy, of a central atom in a molecule or crystal is the number of atoms, molecules or ions bonded to it. The ion/molecule/atom surrounding the central ion/molecule/atom is called a ligand. This number is determined somewhat differently for molecules than for crystals. For molecules and polyatomic ions the coordination number of an atom is determined by simply counting the other atoms to which it is bonded (by either single or multiple bonds). For example, [Cr(NH3)2Cl2Br2]− has Cr3+ as its central cation, which has a coordination number of 6 and is described as ''hexacoordinate''. The common coordination numbers are 4, 6 and 8. Molecules, polyatomic ions and coordination complexes In chemistry, coordination number, defined originally in 1893 by Alfred Werner, is the total number of neighbors of a central atom in a molecule or ion. The concept is most commonly applied to coordination ...
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Polyamine
A polyamine is an organic compound having two or more amino groups. Alkyl polyamines occur naturally, but some are synthetic. Alkylpolyamines are colorless, hygroscopic, and water soluble. Near neutral pH, they exist as the ammonium derivatives. Most aromatic polyamines are crystalline solids at room temperature. Natural polyamines Low-molecular-weight linear polyamines are found in all forms of life. The principal examples are the triamine spermidine and the tetraamine spermine. They are structurally and biosynthetically related to the diamines putrescine and cadaverine. Polyamine metabolism is regulated by the activity of the enzyme ornithine decarboxylase (ODC). Polyamines are found in high concentrations in the mammalian brain. File:Spermidine-2D-skeletal.svg, spermidine File:Spermine.svg, spermine Synthetic polyamines Ethyleneamines are a commercially-important class of synthetic polyamines with ethylene ( linkages); global production capacity was estimated at 385,00 ...
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Ferricyanide
Ferricyanide is the name of the anion CN)6sup>3−. It is also called hexacyanoferrate(III) and in rare, but systematic name">systematic nomenclature, hexacyanidoferrate(III). The most common salt of this anion is potassium ferricyanide, a red crystalline material that is used as an oxidant in organic chemistry. Properties e(CN)6sup>3− consists of a Fe3+ center bound in octahedral geometry to six cyanide ligands. The complex has Oh symmetry. The iron is low spin and easily reduced to the related ferrocyanide ion e(CN)6sup>4−, which is a ferrous (Fe2+) derivative. This redox couple is reversible and entails no making or breaking of Fe–C bonds: : e(CN)6sup>3− + e− ⇌ e(CN)6sup>4− This redox couple is a standard in electrochemistry. Compared to main group cyanides like potassium cyanide, ferricyanides are much less toxic because of the strong bond between the cyanide ion (CN−) and the Fe3+. They do react with mineral acids, however, to release highly tox ...
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Proton Coupled Electron Transfer
A Proton-coupled electron transfer (PCET) is a chemical reaction that involves the transfer of electrons and protons from one atom to another. The term was originally coined for single proton, single electron processes that are concerted, but the definition has relaxed to include many related processes. Reactions that involve the concerted shift of a single electron and a single proton are often called Concerted Proton-Electron Transfer or CPET. In PCET, the proton and the electron (i) start from different orbitals and (ii) are transferred to different atomic orbitals. They transfer in a concerted elementary step. CPET contrast to step-wise mechanisms in which the electron and proton are transferred sequentially. :ET : X+ → Xsup>+ + sup>− :PT : X+ → sup>− + Msup>+ :CPET : X+ → + M Examples PCET is thought to be pervasive. Important examples include water oxidation in photosynthesis, nitrogen fixation, oxygen reduction reaction, and the function of hydrogenas ...
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Inner Sphere Electron Transfer
Inner sphere electron transfer (IS ET) or bonded electron transfer is a redox chemical reaction that proceeds via a covalent linkage—a strong electronic interaction—between the oxidant and the reductant reactants. In inner sphere electron transfer, a ligand bridges the two metal redox centers during the electron transfer event. Inner sphere reactions are inhibited by large ligands, which prevent the formation of the crucial bridged intermediate. Thus, inner sphere ET is rare in biological systems, where redox sites are often shielded by bulky proteins. Inner sphere ET is usually used to describe reactions involving transition metal complexes and most of this article is written from this perspective. However, redox centers can consist of organic groups rather than metal centers. The bridging ligand could be virtually any entity that can convey electrons. Typically, such a ligand has more than one lone electron pair, such that it can serve as an electron donor to both the r ...
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Contrast Agent
A contrast agent (or contrast medium) is a substance used to increase the contrast of structures or fluids within the body in medical imaging. Contrast agents absorb or alter external electromagnetism or ultrasound, which is different from radiopharmaceuticals, which emit radiation themselves. In X-ray imaging, contrast agents enhance the radiodensity in a target tissue or structure. In magnetic resonance imaging (MRI), contrast agents shorten (or in some instances increase) the relaxation times of nuclei within body tissues in order to alter the contrast in the image. Contrast agents are commonly used to improve the visibility of blood vessels and the gastrointestinal tract. The types of contrast agent are classified according to their intended imaging modalities. Radiocontrast media For radiography, which is based on X-rays, iodine and barium are the most common types of contrast agent. Various sorts of iodinated contrast agents exist, with variations occurring between the ...
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Associative Substitution
Associative substitution describes a pathway by which compounds interchange ligands. The terminology is typically applied to organometallic and coordination complexes, but resembles the Sn2 mechanism in organic chemistry. The opposite pathway is dissociative substitution, being analogous to the Sn1 pathway. Intermediate pathways exist between the pure associative and pure dissociative pathways, these are called interchange mechanisms. Associative pathways are characterized by binding of the attacking nucleophile to give a discrete, detectable intermediate followed by loss of another ligand. Complexes that undergo associative substitution are either coordinatively unsaturated or contain a ligand that can change its bonding to the metal, e.g. change in hapticity or bending of a nitrogen oxide ligand (NO). In homogeneous catalysis, the associative pathway is desirable because the binding event, and hence the selectivity of the reaction, depends not only on the nature of the me ...
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Metalloprotein
Metalloprotein is a generic term for a protein that contains a metal ion cofactor. A large proportion of all proteins are part of this category. For instance, at least 1000 human proteins (out of ~20,000) contain zinc-binding protein domains although there may be up to 3000 human zinc metalloproteins. Abundance It is estimated that approximately half of all proteins contain a metal. In another estimate, about one quarter to one third of all proteins are proposed to require metals to carry out their functions. Thus, metalloproteins have many different functions in cells, such as storage and transport of proteins, enzymes and signal transduction proteins, or infectious diseases. The abundance of metal binding proteins may be inherent to the amino acids that proteins use, as even artificial proteins without evolutionary history will readily bind metals. Most metals in the human body are bound to proteins. For instance, the relatively high concentration of iron in the human body ...
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Coordination Chemistry
A coordination complex is a chemical compound consisting of a central atom or ion, which is usually metallic and is called the ''coordination centre'', and a surrounding array of chemical bond, bound molecules or ions, that are in turn known as ''ligands'' or complexing agents. Many metal-containing chemical compound, 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 Ligand#Polydentate and polyhapto ligand motifs and nomenclature, polydentate (multiple bonded) ligand is a molecule or ion that bonds to the central atom ...
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