Hexaamminecobalt(III) Chloride
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Hexaamminecobalt(III) chloride is the chemical compound with the formula o(NH3)6l3. It is the chloride salt of the
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 ' ...
o(NH3)6sup>3+, which is considered an archetypal "Werner complex", named after the pioneer of coordination chemistry,
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 ...
. The cation itself is a
metal ammine complex In coordination chemistry, metal ammine complexes are metal complexes containing at least one ammonia () ligand. "Ammine" is spelled this way for historical reasons; in contrast, alkyl or aryl bearing ligands are spelt with a single "m". Almost al ...
with six
ammonia Ammonia is an inorganic chemical compound of nitrogen and hydrogen with the chemical formula, formula . A Binary compounds of hydrogen, stable binary hydride and the simplest pnictogen hydride, ammonia is a colourless gas with a distinctive pu ...
ligand In coordination chemistry, a ligand is an ion or molecule with a 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 el ...
s attached to the
cobalt Cobalt is a chemical element; it has Symbol (chemistry), symbol Co and atomic number 27. As with nickel, cobalt is found in the Earth's crust only in a chemically combined form, save for small deposits found in alloys of natural meteoric iron. ...
(III) ion.


Properties and structure

o(NH3)6sup>3+ is diamagnetic, with a
low-spin Spin states when describing transition metal coordination complexes refers to the potential spin configurations of the central metal's d electrons. For several oxidation states, metals can adopt high-spin and low-spin configurations. The ambiguity ...
3d6
octahedral In geometry, an octahedron (: octahedra or octahedrons) is any polyhedron with eight faces. One special case is the regular octahedron, a Platonic solid composed of eight equilateral triangles, four of which meet at each vertex. Many types of i ...
Co(III) center. The cation obeys the 18-electron rule and is considered to be a classic example of an exchange inert metal complex. As a manifestation of its inertness, o(NH3)6l3 can be recrystallized unchanged from concentrated
hydrochloric acid Hydrochloric acid, also known as muriatic acid or spirits of salt, is an aqueous solution of hydrogen chloride (HCl). It is a colorless solution with a distinctive pungency, pungent smell. It is classified as a acid strength, strong acid. It is ...
: the NH3 is so tightly bound to the Co(III) centers that it does not dissociate to allow its protonation. In contrast, labile metal ammine complexes, such as i(NH3)6l2, react rapidly with acids, reflecting the
lability Lability refers to the degree that something is likely to undergo change. It is the opposite ( antonym) of stability. Biochemistry In reference to biochemistry, this is an important concept as far as kinetics is concerned in metalloprotein ...
of the Ni(II)–NH3 bonds. Upon heating, hexamminecobalt(III) begins to lose some of its ammine ligands, eventually producing a stronger oxidant. The chloride ions in o(NH3)6l3 can be exchanged with a variety of other
anion An ion () is an atom or molecule with a net electrical charge. The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be positive by conven ...
s such as
nitrate Nitrate is a polyatomic ion with the chemical formula . salt (chemistry), Salts containing this ion are called nitrates. Nitrates are common components of fertilizers and explosives. Almost all inorganic nitrates are solubility, soluble in wa ...
,
bromide A bromide ion is the negatively charged form (Br−) of the element bromine, a member of the halogens group on the periodic table. Most bromides are colorless. Bromides have many practical roles, being found in anticonvulsants, flame-retard ...
,
iodide An iodide ion is I−. Compounds with iodine in formal oxidation state −1 are called iodides. In everyday life, iodide is most commonly encountered as a component of iodized salt, which many governments mandate. Worldwide, iodine deficiency ...
, sulfamate to afford the corresponding o(NH3)63 derivative. Such salts are orange or bright yellow and display varying degrees of water solubility. The chloride ion can be also exchanged with more complex anions such as the hexathiocyanatochromate(III), yielding a pink compound with formula o(NH3)6 r(SCN)6 or the
ferricyanide Ferricyanide is the name of the anion CN)6sup>3−. It is also called hexacyanoferrate(III) and in rare, but systematic name">systematic nomenclature, hexacyanidoferrate(III). The most common salt of this anion is potassium ferricyanide, a red ...
ion.


Preparation

o(NH3)6l3 is prepared by treating
cobalt(II) chloride Cobalt(II) chloride is an inorganic compound, a salt of cobalt and chlorine, with the formula . The compound forms several hydrates ·''n'', for ''n'' = 1, 2, 6, and 9. Claims of the formation of tri- and tetrahydrates have not been confirmed.M. ...
with
ammonia Ammonia is an inorganic chemical compound of nitrogen and hydrogen with the chemical formula, formula . A Binary compounds of hydrogen, stable binary hydride and the simplest pnictogen hydride, ammonia is a colourless gas with a distinctive pu ...
and
ammonium chloride Ammonium chloride is an inorganic chemical compound with the chemical formula , also written as . It is an ammonium salt of hydrogen chloride. It consists of ammonium cations and chloride anions . It is a white crystalline salt (chemistry), sal ...
followed by oxidation. Oxidants include
hydrogen peroxide Hydrogen peroxide is a chemical compound with the formula . In its pure form, it is a very pale blue liquid that is slightly more viscosity, viscous than Properties of water, water. It is used as an oxidizer, bleaching agent, and antiseptic, usua ...
or
oxygen Oxygen is a chemical element; it has chemical symbol, symbol O and atomic number 8. It is a member of the chalcogen group (periodic table), group in the periodic table, a highly reactivity (chemistry), reactive nonmetal (chemistry), non ...
in the presence of charcoal catalyst. This salt appears to have been first reported by Fremy. The acetate salt can be prepared by aerobic oxidation of cobalt(II) acetate,
ammonium acetate Ammonium acetate, also known as spirit of Mindererus in aqueous solution, is a chemical compound with the formula NH4CH3CO2. It is a white, hygroscopic solid and can be derived from the reaction of ammonia and acetic acid. It is available commerci ...
, and ammonia in methanol. The acetate salt is highly water-soluble to the level of 1.9 M (20 °C), versus 0.26 M for the trichloride.


Uses in the laboratory

o(NH3)6sup>3+ is a component of some
structural biology Structural biology deals with structural analysis of living material (formed, composed of, and/or maintained and refined by living cells) at every level of organization. Early structural biologists throughout the 19th and early 20th centuries we ...
methods (especially for
DNA Deoxyribonucleic acid (; DNA) is a polymer composed of two polynucleotide chains that coil around each other to form a double helix. The polymer carries genetic instructions for the development, functioning, growth and reproduction of al ...
or
RNA Ribonucleic acid (RNA) is a polymeric molecule that is essential for most biological functions, either by performing the function itself (non-coding RNA) or by forming a template for the production of proteins (messenger RNA). RNA and deoxyrib ...
, where positive ions stabilize tertiary structure of the phosphate backbone), to help solve their structures by
X-ray crystallography X-ray crystallography is the experimental science of determining the atomic and molecular structure of a crystal, in which the crystalline structure causes a beam of incident X-rays to Diffraction, diffract in specific directions. By measuring th ...
or by
nuclear magnetic resonance Nuclear magnetic resonance (NMR) is a physical phenomenon in which nuclei in a strong constant magnetic field are disturbed by a weak oscillating magnetic field (in the near field) and respond by producing an electromagnetic signal with a ...
. In the biological system, the counterions would more probably be Mg2+, but the heavy atoms of cobalt (or sometimes
iridium Iridium is a chemical element; it has the symbol Ir and atomic number 77. This very hard, brittle, silvery-white transition metal of the platinum group, is considered the second-densest naturally occurring metal (after osmium) with a density ...
, as in ) provide
anomalous scattering Anomalous X-ray scattering (AXRS or XRAS) is a non-destructive determination technique within X-ray diffraction that makes use of the anomalous dispersion that occurs when a wavelength is selected that is in the vicinity of an absorption edge of on ...
to solve the
phase problem In physics, the phase problem is the problem of loss of information concerning the phase that can occur when making a physical measurement. The name comes from the field of X-ray crystallography, where the phase problem has to be solved for the de ...
and produce an electron-density map of the structure. o(NH3)6sup>3+ is used to investigate
DNA Deoxyribonucleic acid (; DNA) is a polymer composed of two polynucleotide chains that coil around each other to form a double helix. The polymer carries genetic instructions for the development, functioning, growth and reproduction of al ...
. The cation induces the transition of DNA structure from the classical B-form to the Z-form.


Related compounds

* Tris(ethylenediamine)cobalt(III) chloride


References

{{reflist Cobalt complexes Cobalt(III) compounds Inorganic compounds Chlorides Octahedral compounds Ammine complexes