Iron Tris(diethyldithiocarbamate)
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Iron tris(diethyldithiocarbamate) is the
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 ...
of iron with
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 hydrox ...
with the formula Fe(S2CNEt2)3 (Et =
ethyl Ethyl may refer to: Arts and entertainment * Cold Ethyl, a Swedish rock band *Ethyl Sinclair, a character in the ''Dinosaurs'' television show Science and technology * Ethyl group, an organic chemistry moiety * Ethyl alcohol (or ethanol) * E ...
). 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 Symmetry (from grc, συμμετρία "agreement in dimensions, due proportion, arrangement") in everyday language refers to a sense of harmonious and beautiful proportion and balance. In mathematics, "symmetry" has a more precise definit ...
. The phenomenon of
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 ...
(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 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 ...
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 and a high spin configuration near room temperature. Iron tris(dithiocarbamate)s characteristically react with
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 che ...
to give Fe(dtc)2NO. This efficient
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 trappi ...
ping 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) derivatives e(S2CNR2)3sup>+.


Safety

Iron tris(di''methyl''dithiocarbamate) is the herbicide
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 typica ...
, which is poisonous.


See also

*
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 typica ...
- a related di''methyl''dithiocarbamate complex of iron * Iron bis(diethyldithiocarbamate) *
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 C ...


References

{{reflist Fungicides Dithiocarbamates Iron(III) compounds Iron complexes