Hexaamminecobalt(III) chloride

Last updated
Hexaamminecobalt(III) chloride
CoA6Cl3.svg
Hexamminecobalt(III)Chloride.jpg
Names
IUPAC name
Hexaamminecobalt(III) chloride
Other names
Cobalt hexammine chloride, hexaamminecobalt(III) chloride
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.030.991 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 234-103-9
PubChem CID
UNII
  • InChI=1S/3ClH.Co.6H3N/h3*1H;;6*1H3/q;;;+3;;;;;;/p-3
    Key: JXBGZYGSWFSYFI-UHFFFAOYSA-K
  • [NH3+][Co-3]([NH3+])([NH3+])([NH3+])([NH3+])[NH3+].[Cl-].[Cl-].[Cl-]
Properties
H18N6Cl3Co
Molar mass 267.48 g/mol
Appearanceyellow or orange crystals
Density 1.71 g/cm3,
Melting point decomposes
0.26 M (20 °C)
tribromide: 0.04 M (18 °C)
Solubility soluble in NH3
Structure
octahedral
0 D
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
poison
GHS labelling:
GHS-pictogram-exclam.svg
Warning
H315, H319, H335
P261, P264, P271, P280, P302+P352, P304+P340, P305+P351+P338, P312, P321, P332+P313, P337+P313, P362, P403+P233, P405, P501
Related compounds
Other anions
[Co(NH3)6]Br3
[Co(NH3)6](OAc)3
Other cations
[Cr(NH3)6]Cl3
[Ni(NH3)6]Cl2
Related compounds
[Co(H2NCH2CH2NH2)3]Cl3

[Co(NH3)5(H2O)]Cl3
[Co(NH3)5Cl]Cl2

Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Hexaamminecobalt(III) chloride is the chemical compound with the formula [Co(NH3)6]Cl3. It is the chloride salt of the coordination complex [Co(NH3)6]3+, which is considered an archetypal "Werner complex", named after the pioneer of coordination chemistry, Alfred Werner. The cation itself is a metal ammine complex with six ammonia ligands attached to the cobalt(III) ion.

Contents

Properties and structure

[Co(NH3)6]3+ is diamagnetic, with a low-spin 3d6 octahedral 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, [Co(NH3)6]Cl3 can be recrystallized unchanged from concentrated hydrochloric acid: the NH3 is so tightly bound to the Co(III) centers that it does not dissociate to allow its protonation. [1] In contrast, labile metal ammine complexes, such as [Ni(NH3)6]Cl2, react rapidly with acids, reflecting the lability 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 [Co(NH3)6]Cl3 can be exchanged with a variety of other anions such as nitrate, bromide, iodide, sulfamate to afford the corresponding [Co(NH3)6]X3 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 [Co(NH3)6] [Cr(SCN)6], or the ferricyanide ion.[ citation needed ]

Preparation

[Co(NH3)6]Cl3 is prepared by treating cobalt(II) chloride with ammonia and ammonium chloride followed by oxidation. Oxidants include hydrogen peroxide or oxygen in the presence of charcoal catalyst. [1] This salt appears to have been first reported by Fremy. [2]

The acetate salt can be prepared by aerobic oxidation of cobalt(II) acetate, ammonium acetate, and ammonia in methanol. [3] 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

[Co(NH3)6]3+ is a component of some structural biology methods (especially for DNA or RNA, where positive ions stabilize tertiary structure of the phosphate backbone), to help solve their structures by X-ray crystallography [4] or by nuclear magnetic resonance. [5] In the biological system, the counterions would more probably be Mg2+, but the heavy atoms of cobalt (or sometimes iridium, as in PDB: 2GIS ) provide anomalous scattering to solve the phase problem and produce an electron-density map of the structure. [6]

[Co(NH3)6]3+ is used to investigate DNA. The cation induces the transition of DNA structure from the classical B-form to the Z-form. [7]

Related Research Articles

<span class="mw-page-title-main">Coordination complex</span> Molecule or ion containing ligands datively bonded to a central metallic atom

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 bound molecules or ions, that are in turn known as ligands or complexing agents. Many metal-containing compounds, especially those that include transition metals, are coordination complexes.

<span class="mw-page-title-main">Ammonium</span> Chemical compound

Ammonium is a modified form of ammonia that has an extra hydrogen atom. It is a positively charged (cationic) molecular ion with the chemical formula NH+4 or [NH4]+. It is formed by the addition of a proton to ammonia. Ammonium is also a general name for positively charged (protonated) substituted amines and quaternary ammonium cations, where one or more hydrogen atoms are replaced by organic or other groups. Not only is ammonium a source of nitrogen and a key metabolite for many living organisms, but it is an integral part of the global nitrogen cycle. As such, human impact in recent years could have an effect on the biological communities that depend on it.

<span class="mw-page-title-main">Alfred Werner</span> Swiss chemist (1866–1919)

Alfred Werner 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 of transition metal complexes. Werner developed the basis for modern coordination chemistry. He was the first inorganic chemist to win the Nobel Prize, and the only one prior to 1973.

Neodymium(III) chloride or neodymium trichloride is a chemical compound of neodymium and chlorine with the formula NdCl3. This anhydrous compound is a mauve-colored solid that rapidly absorbs water on exposure to air to form a purple-colored hexahydrate, NdCl3·6H2O. Neodymium(III) chloride is produced from minerals monazite and bastnäsite using a complex multistage extraction process. The chloride has several important applications as an intermediate chemical for production of neodymium metal and neodymium-based lasers and optical fibers. Other applications include a catalyst in organic synthesis and in decomposition of waste water contamination, corrosion protection of aluminium and its alloys, and fluorescent labeling of organic molecules (DNA).

<span class="mw-page-title-main">Rhodium(III) chloride</span> Chemical compound

Rhodium(III) chloride refers to inorganic compounds with the formula RhCl3(H2O)n, where n varies from 0 to 3. These are diamagnetic red-brown solids. The soluble trihydrated (n = 3) salt is the usual compound of commerce. It is widely used to prepare compounds used in homogeneous catalysis.

<span class="mw-page-title-main">Iridium(III) chloride</span> Chemical compound

Iridium(III) chloride is the inorganic compound with the formula IrCl3. The anhydrous compound is relatively rare, but the related hydrate is much more commonly encountered. The anhydrous salt has two polymorphs, α and β, which are brown and red colored respectively. More commonly encountered is the hygroscopic dark green trihydrate IrCl3(H2O)3 which is a common starting point for iridium chemistry.

<span class="mw-page-title-main">Metal ammine complex</span> Class of chemical compounds

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 all metal ions bind ammonia as a ligand, but the most prevalent examples of ammine complexes are for Cr(III), Co(III), Ni(II), Cu(II) as well as several platinum group metals.

<span class="mw-page-title-main">Hexol</span> Chemical compound

In chemistry, hexol is a cation with formula {[Co(NH3)4(OH)2]3Co}6+ — a coordination complex consisting of four cobalt cations in oxidation state +3, twelve ammonia molecules NH
3
, and six hydroxy anions HO
, with a net charge of +6. The hydroxy groups act as bridges between the central cobalt atom and the other three, which carry the ammonia ligands.

Titanium(III) chloride is the inorganic compound with the formula TiCl3. At least four distinct species have this formula; additionally hydrated derivatives are known. TiCl3 is one of the most common halides of titanium and is an important catalyst for the manufacture of polyolefins.

<span class="mw-page-title-main">Ytterbium(III) chloride</span> Chemical compound

Ytterbium(III) chloride (YbCl3) is an inorganic chemical compound. It reacts with NiCl2 to form a very effective catalyst for the reductive dehalogenation of aryl halides. It is poisonous if injected, and mildly toxic by ingestion. It is an experimental teratogen, known to irritate the skin and eyes.

<span class="mw-page-title-main">Hexafluorophosphate</span> Anion with the chemical formula PF6–

Hexafluorophosphate is an anion with chemical formula of [PF6]. It is an octahedral species that imparts no color to its salts. [PF6] is isoelectronic with sulfur hexafluoride, SF6, and the hexafluorosilicate dianion, [SiF6]2−, and hexafluoroantimonate [SbF6]. In this anion, phosphorus has a valence of 5. Being poorly nucleophilic, hexafluorophosphate is classified as a non-coordinating anion.

There are three sets of Indium halides, the trihalides, the monohalides, and several intermediate halides. In the monohalides the oxidation state of indium is +1 and their proper names are indium(I) fluoride, indium(I) chloride, indium(I) bromide and indium(I) iodide.

<span class="mw-page-title-main">Potassium tetrachloroplatinate</span> Chemical compound

Potassium tetrachloroplatinate(II) is the chemical compound with the formula K2PtCl4. This reddish orange salt is an important reagent for the preparation of other coordination complexes of platinum. It consists of potassium cations and the square planar dianion PtCl42−. Related salts are also known including Na2PtCl4, which is brown-colored and soluble in alcohols, and quaternary ammonium salts, which are soluble in a broader range of organic solvents.

<span class="mw-page-title-main">Tris(ethylenediamine)cobalt(III) chloride</span> Chemical compound

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.

<span class="mw-page-title-main">Chloropentamminecobalt chloride</span> Cobalt compound

Chloropentamminecobalt chloride is the dichloride salt of the coordination complex [Co(NH3)5Cl]2+. It is a red-violet, diamagnetic, water-soluble salt. The compound has been of academic and historical interest.

<span class="mw-page-title-main">Ammonium carbamate</span> Chemical compound

Ammonium carbamate is a chemical compound with the formula [NH4][H2NCO2] consisting of ammonium cation NH+4 and carbamate anion NH2COO. It is a white solid that is extremely soluble in water, less so in alcohol. Ammonium carbamate can be formed by the reaction of ammonia NH3 with carbon dioxide CO2, and will slowly decompose to those gases at ordinary temperatures and pressures. It is an intermediate in the industrial synthesis of urea (NH2)2CO, an important fertilizer.

<span class="mw-page-title-main">Bromopentaamminecobalt(III) bromide</span> Chemical compound

Bromopentaamminecobalt(III) bromide is the dibromide salt of the cobalt coordination compound with the formula [Co(NH3)5Br]2+. It is a purple, water-soluble solid. The analogous chloropentaamminecobalt(III) chloride is also well known.

Cobalt(III) chloride or cobaltic chloride is an unstable and elusive compound of cobalt and chlorine with formula CoCl
3
. In this compound, the cobalt atoms have a formal charge of +3.

<span class="mw-page-title-main">Transition metal nitrite complex</span> Chemical complexes containing one or more –NO₂ ligands

In organometallic chemistry, transition metal complexes of nitrite describes families of coordination complexes containing one or more nitrite ligands. Although the synthetic derivatives are only of scholarly interest, metal-nitrite complexes occur in several enzymes that participate in the nitrogen cycle.

<span class="mw-page-title-main">Sodium tris(carbonato)cobalt(III)</span> Chemical compound

Sodium tris(carbonato)cobalt(III) is the inorganic compound with the formula Na3Co(CO3)3•3H2O. The salt contains an olive-green metastable cobalt(III) coordination complex. The salt, a homoleptic metal carbonato complex, is sometimes referred to as the “Field-Durrant precursor” and is prepared by the “Field-Durrant synthesis”. It is used in the synthesis of other cobalt(III) complexes. Otherwise cobalt(III) complexes are generated from cobalt(II) precursors, a process that requires an oxidant.

References

  1. 1 2 Bjerrum, J.; McReynolds, J. P. (1946). "Hexamminecobalt(III) Salts". Inorg. Synth. 2: 216–221. doi:10.1002/9780470132333.ch69.
  2. Fremy, M. E. (1852). "Recherches sur le cobalt". Ann. Chim. Phys. 35: 257–312.
  3. Lindholm, R. D.; Bause, Daniel E. (1978). "Complexes of Cobalt Containing Ammonia or Ethylene Diamine: Hexaamminecobalt(III) Salts". Inorg. Synth. 18: 67–69. doi:10.1002/9780470132494.ch14.
  4. Ramakrishnan, B.; Sekharudu, C.; Pan, B.; Sundaralingam, M. (2003). "Near-atomic resolution crystal structure of an A-DNA decamer d(CCCGATCGGG): cobalt hexammine interaction with A-DNA". Acta Crystallogr. D59 (Pt 1): 67–72. Bibcode:2003AcCrD..59...67R. doi:10.1107/s0907444902018917. PMID   12499541.
  5. Rudisser, S.; Tinoco, I. Jr. (2000). "Solution structure of Cobalt(III)hexammine complexed to the GAAA tetraloop, and metal-ion binding to G.A mismatches". J. Mol. Biol. 295 (5): 1211–1232. doi:10.1006/jmbi.1999.3421. PMID   10653698.
  6. McPherson, Alexander (2002). Introduction to Macromolecular Crystallography. John Wiley & Sons. ISBN   0-471-25122-4.
  7. Brennant, R. G.; Westhof, E.; Sundaralingam, M. (1986). "Structure of a Z-DNA with Two Different Backbone Chain Conformations. Stabilization of the Decadeoxyoligonucleotide d(CGTACGTACG) by [CO(NH3)6]3+Binding to the Guanine". Journal of Biomolecular Structure and Dynamics. 3 (4): 649–665. doi:10.1080/07391102.1986.10508453. PMID   3271042.