Ligands
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Ligands
In coordination chemistry, a ligand is an ion or molecule (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 bases. The nature of metal–ligand bonding can range from covalent to 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 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 of the central atom, including ligand substitution rates, the reactivity of the ligands themselves, and redox. Ligand selection requires critical consideration in many practical areas, including bioinorganic and medicinal chemistry, homogeneous catalysis, and environmental chemis ...
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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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Coordination Complex
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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Ligand Cone Angle
In coordination chemistry, the ligand cone angle (a common example being the Tolman cone angle or ''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 and the outermost edge of the van der Waals spheres of the ligand atoms at the perimeter of the cone (see figure). 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, th ...
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Denticity
In coordination chemistry, denticity () refers to the number of donor groups in a given ligand that bind to the central metal atom in a coordination complex. In many cases, only one atom in the ligand binds to the metal, so the denticity equals one, and the ligand is said to be monodentate (sometimes called unidentate). Ligands with more than one bonded atom are called polydentate or multidentate. The denticity of a ligand is described with the Greek letter κ ('kappa'). For example, κ6-EDTA describes an EDTA ligand that coordinates through 6 non-contiguous atoms. Denticity is different from hapticity because hapticity refers exclusively to ligands where the coordinating atoms are contiguous. In these cases the η ('eta') notation is used. Bridging ligands use the μ ('mu') notation. Classes Polydentate ligands are chelating agents and classified by their denticity. Some atoms cannot form the maximum possible number of bonds a ligand could make. In that case one or mor ...
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Isomer
In chemistry, isomers are molecules or polyatomic ions with identical molecular formulae – that is, same number of atoms of each element – but distinct arrangements of atoms in space. Isomerism is existence or possibility of isomers. Isomers do not necessarily share similar chemical or physical properties. Two main forms of isomerism are structural or constitutional isomerism, in which ''bonds'' between the atoms differ; and stereoisomerism or spatial isomerism, in which the bonds are the same but the ''relative positions'' of the atoms differ. Isomeric relationships form a hierarchy. Two chemicals might be the same constitutional isomer, but upon deeper analysis be stereoisomers of each other. Two molecules that are the same stereoisomer as each other might be in different conformational forms or be different isotopologues. The depth of analysis depends on the field of study or the chemical and physical properties of interest. The English word "isomer" () is a back-for ...
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Hapticity
In coordination chemistry, hapticity is the coordination of a ligand to a metal center via an uninterrupted and contiguous series of atoms. The hapticity of a ligand is described with the Greek letter η ('eta'). For example, η2 describes a ligand that coordinates through 2 contiguous atoms. In general the η-notation only applies when multiple atoms are coordinated (otherwise the κ-notation is used). In addition, if the ligand coordinates through multiple atoms that are not contiguous then this is considered denticity (not hapticity), and the κ-notation is used once again. When naming complexes care should be taken not to confuse η with μ ('mu'), which relates to bridging ligands. History The need for additional nomenclature for organometallic compounds became apparent in the mid-1950s when Dunitz, Orgel, and Rich described the structure of the "sandwich complex" ferrocene by X-ray crystallography where an iron atom is ''"sandwiched"'' between two parallel cyclopen ...
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Prussian Blue
Prussian blue (also known as Berlin blue, Brandenburg blue or, in painting, Parisian or Paris blue) is a dark blue pigment produced by oxidation of ferrous ferrocyanide salts. It has the chemical formula Fe CN)">Cyanide.html" ;"title="e(Cyanide">CN) Turnbull's blue is chemically identical, but is made from different reagents, and its slightly different color stems from different impurities and particle sizes. Prussian blue was the first modern synthetic pigment. It is prepared as a very fine colloidal dispersion, because the compound is not soluble in water. It contains variable amounts of other ions and its appearance depends sensitively on the size of the colloidal particles. The pigment is used in paints, and it is the traditional "blue" in blueprints, and became prominent in 19th-century () Japanese woodblock prints. In medicine, orally administered Prussian blue is used as an antidote for certain kinds of heavy metal poisoning, e.g., by thallium(I) and radioactive is ...
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Copper(II) Sulfate
Copper(II) sulfate, also known as copper sulphate, is an inorganic compound with the chemical formula . It forms hydrates , where ''n'' can range from 1 to 7. The pentahydrate (''n'' = 5), a bright blue crystal, is the most commonly encountered hydrate of copper(II) sulfate. Older names for the pentahydrate include blue vitriol, bluestone, vitriol of copper,Antoine-François de Fourcroy, tr. by Robert Heron (1796) "Elements of Chemistry, and Natural History: To which is Prefixed the Philosophy of Chemistry". J. Murray and others, Edinburgh. Page 348. and Roman vitriol.Oxford University Press,Roman vitriol, Oxford Living Dictionaries. Accessed on 2016-11-13 It exothermically dissolves in water to give the aquo complex , which has octahedral molecular geometry. The structure of the solid pentahydrate reveals a polymeric structure wherein copper is again octahedral but bound to four water ligands. The centers are interconnected by sulfate anions to form chains. Anhydrous copper sulfa ...
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Alfred Werner
Alfred Werner (12 December 1866 – 15 November 1919) was a Swiss chemist who was a student at ETH Zurich and a professor at the University of Zurich. He won the Nobel Prize in Chemistry in 1913 for proposing the octahedral configuration of transition metal complexes. Werner developed the basis for modern coordination chemistry. He was the first inorganic chemist to win the Nobel prize, and the only one prior to 1973.https://www.nobelprize.org/nobel_prizes/chemistry/laureates/1913/werner-bio.html Nobel Prize Retrieved 1 December 2012 Biography Werner was born in 1866 in Mulhouse, Alsace (which was then part of France, but which was annexed by Germany in 1871). He was raised as Roman Catholic. He was the fourth and last child of Jean-Adam Werner, a foundry worker, and his second wife, Salomé Jeanette Werner, who originated from a wealthy family. He went to Switzerland to study chemistry at the Swiss Federal Institute (Polytechnikum) in Zurich, but since this institute was n ...
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Octahedral Geometry
In chemistry, octahedral molecular geometry, also called square bipyramidal, describes the shape of compounds with six atoms or groups of atoms or ligands symmetrically arranged around a central atom, defining the vertices of an octahedron. The octahedron has eight faces, hence the prefix ''octa''. The octahedron is one of the Platonic solids, although octahedral molecules typically have an atom in their centre and no bonds between the ligand atoms. A perfect octahedron belongs to the point group Oh. Examples of octahedral compounds are sulfur hexafluoride SF6 and molybdenum hexacarbonyl Mo(CO)6. The term "octahedral" is used somewhat loosely by chemists, focusing on the geometry of the bonds to the central atom and not considering differences among the ligands themselves. For example, , which is not octahedral in the mathematical sense due to the orientation of the bonds, is referred to as octahedral. The concept of octahedral coordination geometry was developed by Alfred Werner ...
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Hexol
In chemistry, hexol is a cation with formula 6+ — a coordination complex consisting of four cobalt cations in oxidation state +3, twelve ammonia molecules , and six hydroxy anions , with a net charge of +6. The hydroxy groups act as bridges between the central cobalt atom and the other three, which carry the ammonia ligands. Salts of hexol, such as the sulfate (SO4)3(H2O)x, are of historical significance as the first synthetic non-carbon-containing chiral compounds. Preparation Salts of hexol were first described by Jørgensen, although it was Werner who recognized its structure. The cation is prepared by heating a solution containing the ''cis''-diaquotetramminecobalt(III) cation o(NH3)4(H2O)2sup>3+ with a dilute base: :4 o(NH3)4(H2O)2sup>3+ + 2 HO− → 6+ + 4 NH4+ + 4 H2O Hexol sulfate Starting with the sulfate and using ammonium hydroxide as the base, depending on the conditions, one obtains the 9-hydrate, the 6-hydrate, or the 4-hydrate of hexol sulfate. Th ...
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