Cobalt compounds

Cobalt compounds are chemical compounds formed by cobalt with other elements. In the compound, the most stable oxidation state of cobalt is the +2 oxidation state, and in the presence of specific ligands, there are also stable compounds with +3 valence. In addition, there are cobalt compounds in high oxidation states +4, +5 and low oxidation states -1, 0, +1.

Inorganic compounds

Halides

Four halides of cobalt(II) are known, which are cobalt(II) fluoride (CoF₂) which is a pink solid, cobalt(II) chloride (CoCl₂) which is a blue solid, cobalt(II) bromide (CoBr₂) which is a green solid, and cobalt(II) iodide (CoI₂) which is a blue-black solid. In addition to the anhydrous forms, these cobalt halides also have hydrates. Anhydrous cobalt(II) chloride is blue, while the hexahydrate is red-purple. Because the color change of cobalt(II) chloride in different hydrates, it can be used to manufacture color-changing silica gel.

Anhydrous cobalt halides react with nitric oxide at 70~120 °C to generate o(NO)₂Xsub>2 (X = Cl, Br or I). The complex of cobalt halides and triethylphosphine ((C₂H₅)₃P) can absorb nitric monoxide in benzene to form the diamagnetic material Co(NO)X₂(P(C₂H₅)₃)申泮文 等. 无机化学丛书 第九卷 锰分族 铁系 铂系. 科学出版社, 2017. ISBN 9787030305459

In the reaction + e⁻ → , the potential is +1.92 V, which is higher than that of Cl₂ to Cl⁻ (+1.36 V). Therefore, the interaction of Co³⁺ with Cl− produces Co²⁺ and releases chlorine gas. The potential from F₂ to F⁻ is as high as +2.87 V, and cobalt(III) fluoride (CoF₃) can exist stably. It is a fluorinated reagent and reacts violently with water.

Oxides and hydroxides

Cobalt can form various oxides, such as CoO, Co₂O₃ and Co₃O₄. Co₃O₄, at 950 °C, decomposes to CoO.

Soluble cobalt salts react with sodium hydroxide to obtain cobalt(II) hydroxide (Co(OH)₂):
: Co(NO₃)₂ + 2 NaOH → Co(OH)₂↓ + 2 NaNO₃

Cobalt(II) hydroxide can be oxidized to the Co(III) compound CoO(OH) under alkaline conditions.

Nitrides

Cobalt powder reacts with ammonia to form two kinds of nitrides, Co₂N and Co₃N. Cobalt reacts with phosphorus or arsenic to form Co₂P, CoP, CoAs₂ and other substances. Cobalt(II) azide (Co(N₃)₂) is another binary compound of cobalt and nitrogen that can explode when heated. Cobalt(II) and azide can form complexes. Cobalt pentazolide Co(N₅)₂ was discovered in 2017, and it exists in the form of the hydrate o(H₂O)₄(N₅)₂�4H₂O. It decomposes at 50~145 °C to form cobalt(II) azide, becoming anhydrous and releasing nitrogen, and exploding when heated further. This compound can be obtained by reacting (N₅)₆(H₃O)₃(NH₄)₄Cl or Na(H₂O)(N₅)]·2H₂OYuangang Xu, ''et al''. A series of energetic metal pentazolate hydrates. ''Nature''. 2017. DOI: 10.1038/nature23662 and cobalt(II) nitrate">[Co(H₂O)₆NO₃)₂ at room temperature. Hydrogen bonding of water stabilizes this molecule.

Cobalt can easily react with nitric acid to form cobalt(II) nitrate Co(NO₃)₂. Cobalt(II) nitrate exists in the anhydrous form and the hydrate form, of which the hexahydrate is the most common. Cobalt nitrate hexahydrate (Co(NO₃)₂·6H₂O) is a red deliquescence crystal that is easily soluble in water, and its molecule contains cobalt(II) hydrated ions ( o(H₂O)₆sup>2+) and free nitrate ions. It can be obtained by precipitation from solution.

Coordination compounds

As for all metals, molecular compounds and polyatomic ions of cobalt are classified as coordination complexes, that is, molecules or ions that contain cobalt linked to one or more ligands. These can be combinations of a potentially infinite variety of molecules and ions, such as:
* water , as in the cation hexaaquocobalt(II) . This pink-colored complex is the predominant cation in solid cobalt sulfate ·_''x'', with ''x'' = 6 or 7, as well as in water solutions thereof.
* ammonia , as in ''cis''-diaquotetraamminecobalt(III) , in hexol , in (the anion of Erdmann's salt),Thomas P. McCutcheon and William J. Schuele (1953): "Complex Acids of Cobalt and Chromium. The Green Carbonatocobalt(III) Anion". ''Journal of the American Chemical Society'', volume 75, issue 8, pages 1845–1846. and in .
* carbonate , as in the green triscarbonatocobaltate(III) anion.H. F. Bauer and W. C. Drinkard (1960): "A General Synthesis of Cobalt(III) Complexes; A New Intermediate, Na3o(CO3)3�3H2O". ''Journal of the American Chemical Society'', volume 82, issue 19, pages 5031–5032. .Fikru Tafesse, Elias Aphane, and Elizabeth Mongadi (2009): "Determination of the structural formula of sodium tris-carbonatocobaltate(III), Na3o(CO3)3�3H2O by thermogravimetry". ''Journal of Thermal Analysis and Calorimetry'', volume 102, issue 1, pages 91–97.
* nitrite as in .
* hydroxide , as in hexol.
* chloride , as in tetrachloridocobaltate(II) .
* bicarbonate , as in .
* oxalate , as in trisoxalatocobaltate(III) .

These attached groups affect the stability of oxidation states of the cobalt atoms, according to general principles of electronegativity and of the hardness–softness. For example, Co³⁺ complexes tend to have ammine ligands. Because phosphorus is softer than nitrogen, phosphine ligands tend to feature the softer Co²⁺ and Co⁺, an example being tris(triphenylphosphine)cobalt(I) chloride (). The more electronegative (and harder) oxide and fluoride can stabilize Co⁴⁺ and Co⁵⁺ derivatives, e.g. caesium hexafluorocobaltate(IV) (Cs₂CoF₆) and potassium percobaltate (K₃CoO₄).

Alfred Werner, a Nobel-prize winning pioneer in coordination chemistry, worked with compounds of empirical formula . One of the isomers determined was cobalt(III) hexammine chloride. This coordination complex, a typical Werner-type complex, consists of a central cobalt atom coordinated by six ammine orthogonal ligands and three chloride counteranions. Using chelating ethylenediamine ligands in place of ammonia gives tris(ethylenediamine)cobalt(III) (), which was one of the first coordination complexes to be resolved into optical isomers. The complex exists in the right- and left-handed forms of a "three-bladed propeller". This complex was first isolated by Werner as yellow-gold needle-like crystals.

Organic compounds

Vitamin B12 is a cobalt-centered organic biomolecule, soluble in water, and involved in the methylation and synthesis of nucleic acid and neurotransmitter. The main source is the offal or meat of herbivorous animals.

Dicobalt octacarbonyl (Co₂(CO)₈) is an orange-red crystal with two isomers in solution:
:
It reacts with hydrogen or sodium to form HCo(CO)₄ or NaCo(CO)₄. It is a catalyst in carbonylation and hydrosilylation reactions.

Cobaltocene (Co(C₅H₅)₂) is a cyclopentadiene complex of cobalt. It has 19 valence electrons and is easily oxidized to with a stable structure of 18 electrons by reaction. It is a structural analog to ferrocene, with cobalt in place of iron. Cobaltocene is much more sensitive to oxidation than ferrocene.

See also

* Nickel compounds

References

{{Chemical compounds by element

Cobalt compounds
Chemical compounds by element