Clathrochelate
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Clathrochelate
In coordination chemistry, clathrochelates are ligands that encapsulate metal ions. Chelating ligands bind to metals more strongly than related monodentate ligands, and macrocyclic ligands bind more strongly than typical chelating ligands. It follows that bi- or polymacrocyclic ligands would bind to metals particularly strongly. Clathrochelates are usually derived from bimacrocyclic ligands. The first examples were derived from the tris( dioximate)s of cobalt(III) and iron(II). The synthesis entails replacement of the hydrogen-bonded proton center with or group: : Also well known are the clathrochelates called sepulchrates derived from 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 insertion and removal of metals from the bindin ...
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Cryptand
In chemistry, cryptands are a family of synthetic, bicyclic and polycyclic, multidentate ligands for a variety of cations. The Nobel Prize for Chemistry in 1987 was given to Donald J. Cram, Jean-Marie Lehn, and Charles J. Pedersen for their efforts in discovering and determining uses of cryptands and crown ethers, thus launching the now flourishing field of supramolecular chemistry. The term ''cryptand'' implies that this ligand binds substrates in a crypt, interring the guest as in a burial. These molecules are three-dimensional analogues of crown ethers but are more selective and strong as complexes for the guest ions. The resulting complexes are lipophilic. Structure The most common and most important cryptand is ; the systematic IUPAC name for this compound is 1,10-diaza-4,7,13,16,21,24-hexaoxabicyclo .8.8exacosane. This compound is termed .2.2ryptand, where the numbers indicate the number of ether oxygen atoms (and hence binding sites) in each of the three bridges be ...
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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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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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Molecular Encapsulation
In supramolecular chemistry, molecular encapsulation is the confinement of a guest molecule inside the cavity of a supramolecular host molecule (molecular capsule, molecular container or cage compounds). Examples of supramolecular host molecule include carcerands and endohedral fullerenes. Reactivity of guests An important implication of encapsulation is that the guest behaves differently from the way it would when in solution. The guest molecule tends to be unreactive and often has distinctive spectroscopic signatures. Compounds normally highly unstable in solution, such as arynes or cycloheptatetraene, have been isolated at room temperature when molecularly encapsulated. Examples One of the first examples of encapsulating a structure at the molecular level was demonstrated by Donald Cram and coworkers; they were able to isolate highly unstable, antiaromatic cylobutadiene at room temperature by encapsulating it within a hemicarcerand. Isolation of cyclobutadiene allowed chem ...
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Chelation
Chelation is a type of bonding of ions and molecules to metal ions. It involves the formation or presence of two or more separate coordinate bonds between a Denticity, polydentate (multiple bonded) ligand and a single central metal atom. These ligands are called chelants, chelators, chelating agents, or sequestering agents. They are usually organic compounds, but this is not a necessity, as in the case of zinc and its use as a maintenance therapy to prevent the absorption of copper in people with Wilson's disease. Chelation is useful in applications such as providing nutritional supplements, in chelation therapy to remove toxic metals from the body, as contrast medium, contrast agents in MRI, MRI scanning, in manufacturing using homogeneous catalysts, in chemical water treatment to assist in the removal of metals, and in fertilizers. Chelate effect The chelate effect is the greater affinity of chelating ligands for a metal ion than that of similar nonchelating (monodentate ...
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Monodentate Ligand
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 m ...
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Macrocycle
Macrocycles are often described as molecules and ions containing a ring of twelve or more atoms. Classical examples include the crown ethers, calixarenes, porphyrins, and cyclodextrins. Macrocycles describe a large, mature area of chemistry. Synthesis The formation of macrocycles by ring-closure is called macrocylization. Pioneering work was reported for studies on terpenoid macrocycles. The central challenge to macrocyclization is that ring-closing reactions do not favor the formation of large rings. Instead, small rings or polymers tend to form. This kinetic problem can be addressed by using high-dilution reactions, whereby intramolecular processes are favored relative to polymerizations. Some macrocyclizations are favored using template reactions. Templates are ions, molecules, surfaces etc. that bind and pre-organize compounds, guiding them toward formation of a particular ring size. The crown ethers are often generated in the presence of an alkali metal cation, whic ...
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Dimethylglyoxime
Dimethylglyoxime is a chemical compound described by the formula CH3C(NOH)C(NOH)CH3. Its abbreviation is dmgH2 for neutral form, and dmgH− for anionic form, where H stands for hydrogen. This colourless solid is the dioxime derivative of the diketone butane-2,3-dione (also known as diacetyl). DmgH2 is used in the analysis of palladium or nickel. Its coordination complexes are of theoretical interest as models for enzymes and as catalysts. Many related ligands can be prepared from other diketones, e.g. benzil. Preparation Dimethylglyoxime can be prepared from butanone first by reaction with ethyl nitrite to give biacetyl monoxime. The second oxime is installed using sodium hydroxylamine monosulfonate: Complexes Dimethylglyoxime forms complexes with metals including nickel, palladium and cobalt. These complexes are used to separate those cations from solutions of metal salts and in gravimetric analysis. It is also used in precious metals refining to precipitate palladium from ...
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Hydrogen Bond
In chemistry, a hydrogen bond (or H-bond) is a primarily electrostatic force of attraction between a hydrogen (H) atom which is covalently bound to a more electronegative "donor" atom or group (Dn), and another electronegative atom bearing a lone pair of electrons—the hydrogen bond acceptor (Ac). Such an interacting system is generally denoted , where the solid line denotes a polar covalent bond, and the dotted or dashed line indicates the hydrogen bond. The most frequent donor and acceptor atoms are the second-row elements nitrogen (N), oxygen (O), and fluorine (F). Hydrogen bonds can be intermolecular (occurring between separate molecules) or intramolecular (occurring among parts of the same molecule). The energy of a hydrogen bond depends on the geometry, the environment, and the nature of the specific donor and acceptor atoms and can vary between 1 and 40 kcal/mol. This makes them somewhat stronger than a van der Waals interaction, and weaker than fully covalent ...
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Tris(ethylenediamine)cobalt(III) Chloride
Tris(ethylenediamine)cobalt(III) chloride is an inorganic compound with the formula [Co(en)3]Cl3 (where "en" is the abbreviation for ethylenediamine). It is the chloride salt of the coordination complex [Co(en)3]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 cation, 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 [Co(en)2Cl(H2NCH2CH2NH3)]Cl3, which contains a r ...
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