Iron Tris(diethyldithiocarbamate)
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Iron Tris(diethyldithiocarbamate)
Iron tris(diethyldithiocarbamate) is the coordination complex of iron with diethyldithiocarbamate with the formula Fe(S2CNEt2)3 (Et = ethyl). It is a black solid that is soluble in organic solvents. Synthesis, structure, bonding Iron tris(dithiocarbamate)s are typically are prepared by salt metathesis reactions. Iron tris(diethyldithiocarbamate) is an octahedral coordination complex of iron(III) with idealized D3 symmetry. The phenomenon of spin crossover (SCO) was first reported in 1931 by Cambi ''et al.'' who observed anomalous magnetic behavior for the tris(N,N-dialkyldithiocarbamatoiron(III) complexes. The magnetism of these complexes are sensitive to the nature of the amine substituents as well as to temperature. This behavior is consistent with an equilibrium between two or more spin states. In the case of Fe(Et2dtc)3, X-ray crystallography reveals that the Fe-S bonds are 231 pm at 79K but 356 pm at 297 K. These data indicate a low-spin configuration at low temperatures an ...
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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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Diethyldithiocarbamate
Sodium diethyldithiocarbamate is the organosulfur compound with the formula NaS2CN(C2H5)2. It is a pale yellow, water soluble salt. Preparation This salt is obtained by treating carbon disulfide with diethylamine in the presence of sodium hydroxide: :CS2 + HN(C2H5)2 + NaOH → NaS2CN(C2H5)2 + H2O Other dithiocarbamates can be prepared similarly from secondary amines and carbon disulfide. They are used as chelating agents for transition metal ions and as precursors to herbicides and vulcanization reagents. Oxidation to thiuram disulfide Oxidation of sodium diethyldithiocarbamate gives the disulfide, also called a thiuram disulfide (Et = ethyl): :2 NaS2CNEt2 + I2 → Et2NC(S)S-SC(S)NEt2 + 2 NaI Ligand bonding The diethyldithiocarbamate anion forms the basis of transition metal dithiocarbamate complexes. The ligands coordinate to many " softer" metals via the two sulfur atoms. Other more complicated bonding modes are known including binding as unidentate liga ...
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Ethyl Group
In organic chemistry, an ethyl group (abbr. Et) is an alkyl substituent with the formula , derived from ethane (). ''Ethyl'' is used in the International Union of Pure and Applied Chemistry's nomenclature of organic chemistry for a saturated two-carbon moiety in a molecule, while the prefix "''eth-''" is used to indicate the presence of two carbon atoms in the molecule. Ethylation Ethylation is the formation of a compound by introduction of the ethyl group. The most widely practiced example of this reaction is the ethylation of benzene with ethylene to yield ethylbenzene, a precursor to styrene, which is a precursor to polystyrene. Approximately 24.7 million tons of ethylbenzene were produced in 1999. :: Many ethyl-containing compounds are generated by electrophilic ethylation, i.e. treatment of nucleophiles with sources of Et+. Triethyloxonium tetrafluoroborate t3OF4 is such a reagent. For good nucleophiles, less electrophilic reagents are employed, such as ethyl h ...
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Symmetry Group
In group theory, the symmetry group of a geometric object is the group of all transformations under which the object is invariant, endowed with the group operation of composition. Such a transformation is an invertible mapping of the ambient space which takes the object to itself, and which preserves all the relevant structure of the object. A frequent notation for the symmetry group of an object ''X'' is ''G'' = Sym(''X''). For an object in a metric space, its symmetries form a subgroup of the isometry group of the ambient space. This article mainly considers symmetry groups in Euclidean geometry, but the concept may also be studied for more general types of geometric structure. Introduction We consider the "objects" possessing symmetry to be geometric figures, images, and patterns, such as a wallpaper pattern. For symmetry of physical objects, one may also take their physical composition as part of the pattern. (A pattern may be specified formally as a scalar field, a funct ...
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Spin Crossover
Spin crossover (SCO) is a phenomenon that occurs in some metal complexes wherein the spin state of the complex changes due to an external stimulus. The stimuli can include temperature or pressure. Spin crossover is sometimes referred to as spin transition or spin equilibrium behavior. The change in spin state usually involves interchange of low spin (LS) and high spin (HS) configuration. Spin crossover is commonly observed with first row transition metal complexes with a d4 through d7 electron configuration in an octahedral ligand geometry. Spin transition curves typically plot the high-spin molar fraction against temperature. Often a gradual spin transition is followed by an abrupt (ΔT = 10K) transition with hysteresis and a two-step transition. The abruptness with hysteresis indicates cooperativity, or “communication”, between neighboring metal complexes. In the latter case, the material is bistable and can exist in the two different spin states with a different range of ...
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X-ray Crystallography
X-ray crystallography is the experimental science determining the atomic and molecular structure of a crystal, in which the crystalline structure causes a beam of incident X-rays to diffract into many specific directions. By measuring the angles and intensities of these diffracted beams, a crystallographer can produce a three-dimensional picture of the density of electrons within the crystal. From this electron density, the mean positions of the atoms in the crystal can be determined, as well as their chemical bonds, their crystallographic disorder, and various other information. Since many materials can form crystals—such as salts, metals, minerals, semiconductors, as well as various inorganic, organic, and biological molecules—X-ray crystallography has been fundamental in the development of many scientific fields. In its first decades of use, this method determined the size of atoms, the lengths and types of chemical bonds, and the atomic-scale differences among various mat ...
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Nitric Oxide
Nitric oxide (nitrogen oxide or nitrogen monoxide) is a colorless gas with the formula . It is one of the principal oxides of nitrogen. Nitric oxide is a free radical: it has an unpaired electron, which is sometimes denoted by a dot in its chemical formula In chemistry, a chemical formula is a way of presenting information about the chemical proportions of atoms that constitute a particular chemical compound or molecule, using chemical element symbols, numbers, and sometimes also other symbols, ... (•N=O or •NO). Nitric oxide is also a heteronuclear diatomic molecule, a class of molecules whose study spawned early modern molecular orbital theory, theories of chemical bonding. An important Reaction intermediate, intermediate in chemical industry, industrial chemistry, nitric oxide forms in combustion systems and can be generated by lightning in thunderstorms. In mammals, including humans, nitric oxide is a signaling molecule in many physiological and pathological pro ...
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Chemical Trap
In chemistry, a chemical trap is a chemical compound that is used to detect unstable compounds. The method relies on efficiency of bimolecular reactions with reagents to produce a more easily characterize trapped product. In some cases, the trapping agent is used in large excess. Case studies Cyclobutadiene A famous example is the detection of cyclobutadiene released upon oxidation of cyclobutadieneiron tricarbonyl. When this degradation is conducted in the presence of an alkyne, the cyclobutadiene is trapped as a bicyclohexadiene. The requirement for this trapping experiment is that the oxidant (ceric ammonium nitrate) and the trapping agent be mutually compatible. : Diphosphorus Diphosphorus is an old target of chemists since it is the heavy analogue of N2. Its fleeting existence is inferred by the controlled degradation of certain niobium complexes in the presence of trapping agents. Again, a Diels-Alder strategy is employed in the trapping: : Silylene Another classic but e ...
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Ferbam
Iron tris(dimethyldithiocarbamate) is the coordination complex of iron with dimethyldithiocarbamate with the formula Fe(S2CNMe2)3 (Me = methyl). It is marketed as a fungicide. Synthesis, structure, bonding Iron tris(dithiocarbamate)s are typically are prepared by salt metathesis reactions. Iron tris(dimethyldithiocarbamate) is an octahedral coordination complex of iron(III) with D3 symmetry. Spin crossover (SCO) was first observed in 1931 by Cambi ''et al.'' who discovered anomalous magnetic behavior for the tris(N,N-dialkyldithiocarbamatoiron(III) complexes. The spin states of these complexes are sensitive to the nature of the amine substituents. Iron tris(dithiocarbamate)s characteristically react with nitric oxide to give Fe(dtc)2NO. This efficient chemical trapping reaction provides a means to detect NO. Reflecting the strongly donating properties of dithiocarbamate ligands, iron tris(dithiocarbamate)s oxidize at relatively mild potentials to give isolable iron(IV) deri ...
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Iron Tris(dimethyldithiocarbamate)
Iron tris(dimethyldithiocarbamate) is the coordination complex of iron with dimethyldithiocarbamate with the formula Fe(S2CNMe2)3 (Me = methyl). It is marketed as a fungicide. Synthesis, structure, bonding Iron tris(dithiocarbamate)s are typically are prepared by salt metathesis reactions. Iron tris(dimethyldithiocarbamate) is an octahedral coordination complex of iron(III) with D3 symmetry. Spin crossover (SCO) was first observed in 1931 by Cambi ''et al.'' who discovered anomalous magnetic behavior for the tris(N,N-dialkyldithiocarbamatoiron(III) complexes. The spin states of these complexes are sensitive to the nature of the amine substituents. Iron tris(dithiocarbamate)s characteristically react with nitric oxide to give Fe(dtc)2NO. This efficient chemical trapping reaction provides a means to detect NO. Reflecting the strongly donating properties of dithiocarbamate ligands, iron tris(dithiocarbamate)s oxidize at relatively mild potentials to give isolable iron(IV) deri ...
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Iron Bis(diethyldithiocarbamate)
Iron bis(diethyldithiocarbamate) is a coordination complex with the formula where Et = . A red solid, it is representative of several ferrous dithiocarbamates with diverse substituents in place of ethyl. In terms of structure, the species is dimeric, consisting of two pentacoordinate iron(II) centers. It is isostructural with , which in turn is similar to zinc bis(dimethyldithiocarbamate). Reactions The complex reacts with a variety of reagents with concomitant formation of mono-iron derivatives. 9,10-Phenanthroline adds to iron bis(diethyldithiocarbamate) to give the blue-octahedral complex . 3,4-Bis(trifluoromethyl)-1,2-dithiete reacts to give the dithiolene complex . Nitric oxide and carbon monoxide to give the nitrosyl complex and the carbonyl complex {{chem2, Fe(S2CNEt2)2(CO)2, respectively. Related compounds * Iron tris(diethyldithiocarbamate) References Iron compounds ison Ison, ISON or variant, may refer to: Geography * Isön, a small island in lake Storsj ...
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Cobalt Tris(diethyldithiocarbamate)
Cobalt tris(diethyldithiocarbamate) is the coordination complex of cobalt with diethyldithiocarbamate with the formula Co(S2CNEt2)3 (Et = ethyl). It is a diamagnetic green solid that is soluble in organic solvents. Synthesis, structure, bonding Cobalt tris(dithiocarbamate)s are typically are prepared by air-oxidation of mixtures of dithiocarbamate salts and a cobalt(II) nitrate. Cobalt tris(diethyldithiocarbamate) is an octahedral coordination complex of low-spin Co(III) with idealized D3 symmetry. The Co-S distances are 267 pm. Reactions Oxidation of Co(Et2dtc)3 occurs at mild potentials to give the cobalt(IV) derivative. Treatment of Co(Et2dtc)3 with fluoroboric acid Fluoroboric acid or tetrafluoroboric acid (archaically, fluoboric acid) is an inorganic compound with the chemical formula +BF4−], where H+ represents the solvated proton. The solvent can be any suitably Lewis-basic entity. For instance, in w ... results in the removal of 0.5 equiv of ligand giving a binucle ...
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