Thiocyanate Complex
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Thiocyanate Complex
Transition metal complexes of thiocyanate describes coordination complexes containing one or more thiocyanate (SCN−) ligands. The topic also includes transition metal complexes of isothiocyanate. These complexes have few applications but played significant role in the development of coordination chemistry. Structure and bonding Hard metal cations, as classified by HSAB theory, tend to form ''N''-bonded complexes (isothiocyanates), whereas class B or soft metal cations tend to form ''S''-bonded thiocyanate complexes. For the isothiocyanates, the M-N-C angle is usually close to 180°. For the thiocyanates, the M-S-C angle is usually close to 100°. CSD CIF YUNGEW.png, Crystal structure of iII(NCS)6sup>4-, a homoleptic complex of six isothiocyanate ligands. Color code: blue = N, yellow = S. PalenikPdPN SCN NCSic1970.svg, Structure of Pd(Me2N(CH2)3PPh2)(SCN)(NCS) illustrating linkage isomerism of the SCN− ligand. CSD CIF OGAKOX.png, Crystal structure of eIV(NCS)5(SCN)sup>2 ...
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Coordination Complex
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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Aryl Diazonium Salt
Diazonium compounds or diazonium salts are a group of organic compounds sharing a common functional group where R can be any organic group, such as an alkyl or an aryl, and X is an inorganic or organic anion, such as a halide. The parent, compound where R is hydrogen, is diazenylium. Structure and general properties Arene derivatives According to X-ray crystallography the linkage is linear in typical diazonium salts. The bond distance in benzenediazonium tetrafluoroborate is 1.083(3)  Å, which is almost identical to that for dinitrogen molecule (N≡N). The linear free energy constants σm and σp indicate that the diazonium group is strongly electron-withdrawing. Thus, the diazonio-substituted phenols and benzoic acids have greatly reduced p''K''a values compared to their unsubstituted counterparts. The p''K''a of phenolic proton of 4-hydroxybenzenediazonium is 3.4, versus 9.9 for phenol itself. In other words, the diazonium group raises the ionization constant ''K''a ( ...
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Inorganic Chemistry
Inorganic chemistry deals with chemical synthesis, synthesis and behavior of inorganic compound, inorganic and organometallic chemistry, organometallic compounds. This field covers chemical compounds that are not carbon-based, which are the subjects of organic chemistry. The distinction between the two disciplines is far from absolute, as there is much overlap in the subdiscipline of organometallic chemistry. It has applications in every aspect of the chemical industry, including catalysis, materials science, pigments, surfactants, coatings, pharmaceutical drug, medications, fuels, and agriculture. Occurrence Many inorganic compounds are found in nature as minerals. Soil may contain iron sulfide as pyrite or calcium sulfate as gypsum. Inorganic compounds are also found multitasking as biomolecules: as electrolytes (sodium chloride), in energy storage (Adenosine triphosphate, ATP) or in construction (the polyphosphate backbone in DNA). Bonding Inorganic compounds exhibit a range ...
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Thiocyanates
Thiocyanates are salts containing the thiocyanate anion (also known as rhodanide or rhodanate). is the conjugate base of thiocyanic acid. Common salts include the colourless salts potassium thiocyanate and sodium thiocyanate. Mercury(II) thiocyanate was formerly used in pyrotechnics. Thiocyanate is analogous to the cyanate ion, , wherein oxygen is replaced by sulfur. is one of the pseudohalides, due to the similarity of its reactions to that of halide ions. Thiocyanate used to be known as rhodanide (from a Greek word for rose) because of the red colour of its complexes with iron. Thiocyanate is produced by the reaction of elemental sulfur or thiosulfate with cyanide: : : The second reaction is catalyzed by thiosulfate sulfurtransferase, a hepatic mitochondrial enzyme, and by other sulfur transferases, which together are responsible for around 80% of cyanide metabolism in the body. Oxidation of thiocyanate inevitably produces hydrogen sulfate. The other product depend ...
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Thiocyanogen
Thiocyanogen, (SCN)2, is a pseudohalogen derived from the pseudohalide thiocyanate, CNsup>−, with behavior intermediate between dibromine and diiodine. This hexatomic compound exhibits C2 point group symmetry and has the connectivity NCS-SCN. In the lungs, lactoperoxidase may oxidize thiocyanate to thiocyanogen or hypothiocyanite. History Berzelius first proposed that thiocyanogen ought exist as part of his radical theory, but the compound's isolation proved problematic. Liebig pursued a wide variety of synthetic routes for the better part of a century, but, even with Wöhler's assistance, only succeeded in producing a complex mixture with the proportions of thiocyanic acid. In 1861, Linnemann generated appreciable quantities of thiocyanogen from a silver thiocyanate suspension in diethyl ether and excess iodine, but misidentified the minor product as sulfur iodide cyanide (ISCN). Indeed, that reaction suffers from competing equilibria attributed to the weak ox ...
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Potassium Thiocyanate
Potassium thiocyanate is the chemical compound with the molecular formula KSCN. It is an important salt of the thiocyanate anion, one of the pseudohalides. The compound has a low melting point relative to most other inorganic salts. Uses Chemical synthesis Aqueous KSCN reacts almost quantitatively with Pb(NO3)2 to give Pb(SCN)2, which has been used to convert acyl chlorides to isothiocyanates. KSCN converts ethylene carbonate to ethylene sulfide. For this purpose, the KSCN is first melted under vacuum to remove water. In a related reaction, KSCN converts cyclohexene oxide to the corresponding episulfide and KOCN. : KSCN is also the starting product for the synthesis of carbonyl sulfide. Special effects Dilute aqueous KSCN is occasionally used for moderately realistic blood effects in film and theatre. It can be painted onto a surface or kept as a colorless solution. When in contact with ferric chloride solution (or other solutions containing Fe3+), the produc ...
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Ammonium Thiocyanate
Ammonium thiocyanate is an inorganic compound with the formula . It is an ammonium salt of thiocyanic acid. It consists of ammonium cations and thiocyanate anions . Uses Ammonium thiocyanate is used in the manufacture of herbicides, thiourea, and transparent artificial resins; in matches; as a stabilizing agent in photography; in various rustproofing compositions; as an adjuvant in textile dyeing and printing; as a tracer in oil fields; in the separation of hafnium from zirconium (important for the production of hafnium-free zircalloy for use in nuclear fuel cladding), and in titrimetric analyses. In May 1945, USAAF General Victor E. Betrandias advanced a proposal to his superior General Arnold to use of ammonium thiocyanate to reduce rice crops in Japan as part of the bombing raids on their country. Ammonium thiocyanate can also be used to determine the iron content in soft drinks by colorimetry. Ammonium thiocyanate may also be used to separate quinidine, from liquors, ...
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Dissociative Substitution
In chemistry, dissociative substitution describes a reaction pathway by which compounds interchange ligands. The term is typically applied to coordination and organometallic complexes, but resembles the SN1 mechanism in organic chemistry. This pathway can be well described by the ''cis'' effect, or the labilization of CO ligands in the ''cis'' position. The opposite pathway is associative substitution, being analogous to SN2 pathway. Pathways that are intermediate between the pure dissociative and pure associative pathways are called interchange mechanisms. Complexes that undergo dissociative substitution are often coordinatively saturated and often have octahedral molecular geometry. The entropy of activation is characteristically positive for these reactions, which indicates that the disorder of the reacting system increases in the rate-determining step. Kinetics Dissociative pathways are characterized by a rate determining step that involves release of a ligand from t ...
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Cyanate
The cyanate ion is an anion with the chemical formula . It is a resonance of three forms: (61%) ↔ (30%) ↔ (4%). Cyanate is the derived anion of isocyanic acid, H−N=C=O, and its lesser tautomer cyanic acid (a.k.a. cyanol), H−O−C≡N. Any salt containing the ion, such as ammonium cyanate, is called a cyanate. The cyanate ion is an isomer of the much-less-stable fulminate anion, or .William R. Martin and David W. Ball (2019): "Small organic fulminates as high-energy materials. Fulminates of acetylene, ethylene, and allene". ''Journal of Energetic Materials'', volume 31, issue 7, pages 70-79. The cyanate ion is an ambidentate ligand, forming complexes with a metal ion in which either the nitrogen or oxygen atom may be the electron-pair donor. It can also act as a bridging ligand. Compounds that contain the cyanate functional group, −O−C≡N, are known as cyanates or cyanate esters. The cyanate functional group is distinct from the isocyanate functional ...
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Carbonyl Sulfide
Carbonyl sulfide is the chemical compound with the linear formula . It is a colorless flammable gas with an unpleasant odor. It is a linear molecule consisting of a carbonyl double bonded to a sulfur atom. Carbonyl sulfide can be considered to be intermediate between carbon dioxide and carbon disulfide, both of which are valence isoelectronic with it. Occurrence Carbonyl sulfide is the most abundant sulfur compound naturally present in the atmosphere, at , because it is emitted from oceans, volcanoes and deep sea vents. As such, it is a significant compound in the global sulfur cycle. Measurements on the Antarctica ice cores and from air trapped in snow above glaciers ( firn air) have provided a detailed picture of OCS concentrations from 1640 to the present day and allow an understanding of the relative importance of anthropogenic and non-anthropogenic sources of this gas to the atmosphere. Some carbonyl sulfide that is transported into the stratospheric sulfate lay ...
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Thiocyanate Hydrolase
A thiocyanate hydrolase () is an enzyme belonging to the family of hydrolases. The systematic name of this enzyme class is thiocyanate aminohydrolase. This enzyme catalyzes the chemical reaction A chemical reaction is a process that leads to the chemistry, chemical transformation of one set of chemical substances to another. When chemical reactions occur, the atoms are rearranged and the reaction is accompanied by an Gibbs free energy, ...: : The mechanism is proposed to involve a metal thiocyanate complex. Structural studies As of late 2007, 4 structures have been solved for this class of enzymes, with PDB accession codes , , , and . A second thiocyanate hydrolase with copper at its active site catalyzes its conversion to cyanate: : References * * EC 3.5.5 Enzymes of known structure {{3.5-enzyme-stub ...
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Metalloenzyme
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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