Compounds of zinc

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Compounds of zinc are chemical compounds containing the element zinc which is a member of the group 12 of the periodic table. The oxidation state of most compounds is the group oxidation state of +2. Zinc may be classified as a post-transition main group element with zinc(II). Zinc compounds are noteworthy for their nondescript behavior, they are generally colorless (unlike other elements with the oxidation number +2, which are usually white), do not readily engage in redox reactions, and generally adopt symmetrical structures. [1] [2] [3] [4]

Contents

General characteristics

In its compounds, Zn2+ ions have an electronic configuration [Ar] 3d10. As such, its complexes tend to be symmetrical, ZnO and zinc sulfide, ZnS, (zincblende) in which the oxide and sulfide ions are tetrahedrally bound to four zinc ions. Many complexes, such as ZnCl42−, are tetrahedral. Tetrahedrally coordinated zinc is found in metallo-enzymes such as carbonic anhydrase. Six-coordinate octahedral complexes are also common, such as the ion [Zn(H2O)6]2+, which is present when a zinc salts are dissolved in water. Five- and seven-coordination numbers can be imposed by special organic ligands.

Many zinc(II) salts are isomorphous (have the same type of crystal structure) with the corresponding salts of magnesium(II). This parallel results from the fact that Zn2+ and Mg2+ have almost identical ionic radii as well as filled electron shells. That two elements so different in atomic number have the same radius is a consequence of the d-block contraction. Whilst calcium is somewhat larger than magnesium, there is a steady decrease in size as atomic number increases from calcium to zinc.

Zn(II) complexes are kinetically labile, i.e. the Zn-ligand bonds exchange with other ligands rapidly. For this reason, zinc ions are at the catalytic centers in many enzymes.

Zn(I)

Compounds with zinc in the oxidation state +1 are extremely rare. [5] The compounds have the formula RZn2R and they contain a Zn — Zn bond analogous to the metal-metal bond in mercury(I) ion, Hg22+. In this respect zinc is similar to magnesium where low-valent compounds containing a Mg — Mg bond have been characterised. [6]

Other oxidation states

No compounds of zinc in oxidation states other than +1 or +2 are known. Calculations indicate that a zinc compound with the oxidation state of +4 is unlikely to exist. [7]

Colour and magnetism

Zinc chloride Zinc chloride.jpg
Zinc chloride

Zinc compounds, like those of main group elements, are mostly colourless. Exceptions occur when the compound contains a coloured anion or ligand. However, zinc selenide and zinc telluride are both coloured due to charge-transfer processes. Zinc oxide turns yellow when heated due to the loss of some oxygen atoms and formation of a defect structure. Compounds containing zinc are typically diamagnetic, except in cases where the ligand is a radical.

Reactivity of metallic zinc

Zinc is a strong reducing agent with a standard redox potential of −0.76 V. Pure zinc tarnishes rapidly in air, rapidly forming a passive layer. The composition of this layer can be complex, but one constituent is probably basic zinc carbonate, Zn5(OH)6CO3. [8] The reaction of zinc with water is slowed by this passive layer. When this layer is corroded by acids such as hydrochloric acid and sulfuric acid, the reaction proceeds with the evolution of hydrogen gas. [1] [9]

Zn + 2 H+ → Zn2+ + H2

Zinc reacts with alkalis as with acids.

With oxidants such as chalcogens and halogens, Zn forms binary compounds such as ZnS and ZnCl2.

Binary compounds

The Wurtzite structure, showing the tetrahedral environment of both Zn and S atoms Wurtzite polyhedra.png
The Wurtzite structure, showing the tetrahedral environment of both Zn and S atoms
a unit cell of zincblende Sphalerite-unit-cell-depth-fade-3D-balls.png
a unit cell of zincblende

Zinc oxide, ZnO, is the most important manufactured compound of zinc, with a wide variety of uses. [2] It crystallizes with the Wurtzite structure. It is amphoteric, dissolving in acids to give the aqueous Zn2+ ion and in alkali to give the zincate (a.k.a. tetrahydroxozincate) ion, [Zn(OH)4]2−. Zinc hydroxide, Zn(OH)2 is also amphoteric.

Zinc sulfide, ZnS, crystallizes in two closely related structures, the zincblende crystal structure and the Wurtzite crystal structure, which are common structures of compounds with the formula MA. Both Zn and S are tetrahedrally coordinated by the other ion. A useful property of ZnS is its phosphorescence. The other chalcogenides, ZnSe and ZnTe, have applications in electronics and optics. [10]

Of the four zinc halides, ZnF
2 has the most ionic character, whereas the others, ZnCl
2, ZnBr
2, and ZnI
2, have relatively low melting points and are considered to have more covalent character. [2] The pnictogenides Zn
3N
2 (notable for its high melting point [11] ), Zn
3P
2, Zn
3As
2 and Zn
3Sb
2, have various applications. [12] Other binary compounds of zinc include zinc peroxide ZnO
2, zinc hydride ZnH
2, and zinc carbide ZnC
2. [13]

Salts

Zinc nitrate Zn(NO
3)
2 (used as oxidizing agent), zinc chlorate Zn(ClO
3)
2, zinc sulfate ZnSO
4 (known as "white vitriol"), zinc phosphate Zn
3(PO
4)
2 (used as primer pigment), zinc molybdate ZnMoO
4 (used as white pigment), zinc chromate ZnCrO
4 (one of the few colored zinc compounds), zinc arsenite Zn(AsO2)2 (colorless powder) and zinc arsenate octahydrate Zn(AsO
4)
2•8H
2O (white powder, also referred to as koettigite) are a few examples of other common inorganic compounds of zinc. The latter two compounds are both used in insecticides and wood preservatives. [14] One of the simplest examples of an organic compound of zinc is zinc acetate Zn(O
2CCH
3)
2, which has several medicinal applications. Zinc salts are usually fully dissociated in aqueous solution. Exceptions occur when the anion can form a complex, such as in the case of zinc sulfate, where the complex [Zn(H2O)n(SO4] may be formed, (log K = ca. 2.5). [15]

Complexes

Structure of solid basic zinc acetate, [Zn 4(m -O)(e -O 2CCH 3) 6] BasicZnAcetate.png
Structure of solid basic zinc acetate, [Zn
4(μ -O)(η -O
2CCH
3)
6]

The most common structure of zinc complexes is tetrahedral which is clearly connected with the fact that the octet rule is obeyed in these cases. Nevertheless, octahedral complexes comparable to those of the transition elements are not rare. Zn2+ is a class A acceptor in the classification of Ahrland, Chatt and Davies, [16] and so forms stronger complexes with the first-row donor atoms oxygen or nitrogen than with second-row sulfur or phosphorus. In terms of HSAB theory Zn2+ is a hard acid.

In aqueous solution an octahedral complex, [Zn(H2O)6]2+ is the predominant species. [17] Aqueous solutions of zinc salts are mildly acidic because the aqua-ion is subject to hydrolysis with a pKa of around 9, depending on conditions. [18]

[Zn(H2O)6]2+⇌ [Zn(H2O)5(OH)]+ + H+

Hydrolysis explains why basic salts such as basic zinc acetate and basic zinc carbonate, Zn3(OH)4(CO3)•H2O are easy to obtain. The reason for the hydrolysis is the high electrical charge density on the zinc ion, which pulls electrons away from an OH bond of a coordinated water molecule and releases a hydrogen ion. The polarizing effect of Zn2+ is part of the reason why zinc is found in enzymes such as carbonic anhydrase.

Structure of a monomeric zinc dialkyldithiophosphate Zn(dtp)2.png
Structure of a monomeric zinc dialkyldithiophosphate

No fluoro complexes are known, but complexes with the other halides and with pseodohalides, [ZnX3]− and [ZnX4]2− can be prepared. The case of the thiocyanate complex illustrates the class A character of the zinc ion as it is the N-bonded isomer, [Zn(NCS)4]2−in contrast to [Cd(SCN)4]2− which is S-bonded. Being a class-A acceptor does not preclude the formation of complexes with sulfur donors, as is shown by zinc dithiophosphate and the zinc finger complex (below).

The zinc acetylacetonate complex, Zn(acac)2 is interesting. As the ligand is bidentate a tetrahedral structure might be expected. However, the compound is in fact a trimer, Zn3(acac)6 in which each Zn ion is coordinated by five oxygen atoms in a distorted trigonal bipyramidal structure. [2] Other 5-coordinate structures can be designed by choosing ligands which have specific stereochemical requirements. For example, terpyridine, which is a tridentate ligand forms the complex [Zn(terpy)Cl2]. Another example would involve a tripodal ligand such as Tris(2-aminoethyl)amine. Square pyramidal 5-coordinate Zinc is found in Tetra(4-pyridyl)porphinatomonopyridinezinc(II) [19] Solution studies of other 5-coordinate Zinc porphyrins have been reported. [20] [21] The compound zinc cyanide, Zn(CN)2, is not 2-coordinate. It adopts a polymeric structure consisting of tetrahedral zinc centres linked by bridging cyanide ligands. The cyanide group shows head to tail disorder with any zinc atom having between 1 and 4 carbon atom neighbours and the remaining being nitrogen atoms. These two examples illustrate the difficulty of sometimes relating structure to stoichiometry.

A coordination number of 2 occurs in zinc amide Zn(NR1R2)2 (R1=CMe3, R2=SiMe3); the ligand is so bulky that there is not enough space for more than two of them. [22]

Bio-complexes

Carbonic anhydrase: an hydroxide group (red) is shown attached to zinc (gray) Carbonic anhydrase 1CA2 active site.png
Carbonic anhydrase: an hydroxide group (red) is shown attached to zinc (gray)
Zinc finger motif. The zinc ion (green) is coordinated by two histidine residues and two cysteine residues. Zinc finger rendered.png
Zinc finger motif. The zinc ion (green) is coordinated by two histidine residues and two cysteine residues.

A very large number of metallo-enzymes contain zinc(II). Also many proteins contain zinc for structural reasons. The zinc ion is invariably 4-coordinate with at least three ligands that are amino-acid side-chains. The imidazole nitrogen of a histidine side-chain is a common ligand. The following are typical examples of the two kinds of zinc-protein complexes.

In the active site of resting carbonic anhydrase a zinc ion is coordinated by three histidine residues. The fourth position is occupied by a water molecule, which is strongly polarized as in hydrolysis (see above). When carbon dioxide enters the active site, it subject to nucleophilic attack by the oxygen atom which carries a partial negative charge, or indeed a full negative charge if the water molecule is dissociated. The CO2 is rapidly converted into a bicarbonate ion. [23]

[(-hys)3Zn(H2O)]2+ + CO2 → [(-hys)3Zn]2+ + HCO3− + H+

Some peptidases, such as glutamate carboxypeptidase II are thought to act in a similar way, with the zinc ion promoting the formation of a nucleophilic reagent. [23]

The zinc finger motif is a rigid substructure in a protein which facilitates the binding of the protein to another molecule such as DNA. [24] In this case all four coordination positions are occupied by the histidine and cysteine residues. The tetrahedral geometry around the zinc ion constrains an α helix fragment and an antiparallel β sheet fragment to a particular orientation with respect to each other.

The magnesium ion, which has a higher concentration in biological fluids, cannot perform these functions because its complexes are much weaker than those of zinc.

Organometallic compounds

Diethylzinc Diethylzinc structure.png
Diethylzinc

Organozinc compounds contain zinc—carbon covalent bonds. Diethylzinc ((C
2H
5)
2Zn) was first reported in 1848. It was made by reaction of zinc and ethyl iodide and is the first compound known to contain a metal—carbon sigma bond. [25] For a long time it was a mystery why copper(II) did not form an analogous compound. It was not until the 1980s that the reason was found: the zinc compound does not undergo the beta-hydride elimination reaction whereas the compound of the transition metal copper does so. Alkyl and aryl zinc compounds are contain the linear C—Zn—C motif. Because the zinc centre is coordinatively unsaturated, the compounds are powerful electrophiles. In fact the low-molecular weight compounds will ignite spontaneously on contact with air and are immediately destroyed by reaction with water molecules. The use of zinc alkyls has been largely superseded by the use of the more easily handled Grignard reagents. This demonstrates yet another connection between the chemistries of zinc and magnesium.

Zinc cyanide, Zn(CN)
2, is used as a catalyst in some organic reactions. [26]

Organometallic compounds of zinc(I) contain M—M bonds. Decamethyldizincocene is now known. [27]

See also

Related Research Articles

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 of transition metals, are coordination complexes. A coordination complex whose centre is a metal atom is called a metal complex of d block element.

Hydroxide

Hydroxide is a diatomic anion with chemical formula OH−. It consists of an oxygen and hydrogen atom held together by a covalent bond, and carries a negative electric charge. It is an important but usually minor constituent of water. It functions as a base, a ligand, a nucleophile, and a catalyst. The hydroxide ion forms salts, some of which dissociate in aqueous solution, liberating solvated hydroxide ions. Sodium hydroxide is a multi-million-ton per annum commodity chemical. A hydroxide attached to a strongly electropositive center may itself ionize, liberating a hydrogen cation (H+), making the parent compound an acid.

Inorganic chemistry deals with synthesis and behavior of inorganic and organometallic compounds. This field covers all chemical compounds except the myriad of organic compounds, which are the subjects of organic chemistry. The distinction between the two disciplines is far from absolute, as there is much overlap in the subdiscipline of organometallic chemistry. It has applications in every aspect of the chemical industry, including catalysis, materials science, pigments, surfactants, coatings, medications, fuels, and agriculture.

Compounds of carbon are defined as chemical substances containing carbon. More compounds of carbon exist than any other chemical element except for hydrogen. Organic carbon compounds are far more numerous than inorganic carbon compounds. In general bonds of carbon with other elements are covalent bonds. Carbon is tetravalent but carbon free radicals and carbenes occur as short-lived intermediates. Ions of carbon are carbocations and carbanions are also short-lived. An important carbon property is catenation as the ability to form long carbon chains and rings.

Ligand

In coordination chemistry, a ligand is an ion or molecule 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 electron pairs. The nature of metal–ligand bonding can range from covalent to ionic. Furthermore, the metal–ligand bond order can range from one to three. Ligands are viewed as Lewis bases, although rare cases are known to involve Lewis acidic "ligands".

Sulfate Oxyanion with a central atom of sulfur surrounded by 4 oxygen atoms

The sulfate or sulphate ion is a polyatomic anion with the empirical formula SO2−
4.Salts, acid derivatives, and peroxides of sulfate are widely used in industry. Sulfates occur widely in everyday life. Sulfates are salts of sulfuric acid and many are prepared from that acid.

In chemistry, an amphoteric compound is a molecule or ion that can react both as an acid and as a base. What exactly this can mean depends on which definitions of acids and bases are being used. The prefix of the word 'amphoteric' is derived from a Greek prefix amphi-, which means both.

Metalloprotein Protein that contains a metal ion cofactor

Metalloprotein is a generic term for a protein that contains a metal ion cofactor. A large proportion of all proteins are part of this category. For instance, at least 1000 human proteins contain zinc-binding protein domains although there may be up to 3000 human zinc metalloproteins.

Zinc chloride

Zinc chloride is the name of chemical compounds with the formula ZnCl2 and its hydrates. Zinc chlorides, of which nine crystalline forms are known, are colorless or white, and are highly soluble in water. ZnCl2 itself is hygroscopic and even deliquescent. Samples should therefore be protected from sources of moisture, including the water vapor present in ambient air. Zinc chloride finds wide application in textile processing, metallurgical fluxes, and chemical synthesis. No mineral with this chemical composition is known aside from the very rare mineral simonkolleite, Zn5(OH)8Cl2·H2O.

Titanium tetrachloride

Titanium tetrachloride is the inorganic compound with the formula TiCl4. It is an important intermediate in the production of titanium metal and the pigment titanium dioxide. TiCl4 is a volatile liquid. Upon contact with humid air, it forms spectacular opaque clouds of titanium dioxide (TiO2) and hydrated hydrogen chloride. It is sometimes referred to as "tickle" or "tickle 4" due to the phonetic resemblance of its molecular formula (TiCl4) to the word.

Uranyl

The uranyl ion is an oxycation of uranium in the oxidation state +6, with the chemical formula UO2+
2. It has a linear structure with short U–O bonds, indicative of the presence of multiple bonds between uranium and oxygen. Four or more ligands may be bound to the uranyl ion in an equatorial plane around the uranium atom. The uranyl ion forms many complexes, particularly with ligands that have oxygen donor atoms. Complexes of the uranyl ion are important in the extraction of uranium from its ores and in nuclear fuel reprocessing.

Zinc cyanide

Zinc cyanide is the inorganic compound with the formula Zn(CN)2. It is a white solid that is used mainly for electroplating zinc but also has more specialized applications for the synthesis of organic compounds.

Zinc nitrate

Zinc nitrate is an inorganic chemical compound with the formula Zn(NO3)2. This white, crystalline solid is highly deliquescent and is typically encountered as a hexahydrate Zn(NO3)2•6H2O. It is soluble in both water and alcohol.

Keggin structure

Keggin structure is the best known structural form for heteropoly acids. It is the structural form of α-Keggin anions, which have a general formula of [XM12O40]n−, where X is the heteroatom (most commonly are P5+, Si4+, or B3+), M is the addenda atom (most common are molybdenum and tungsten), and O represents oxygen. The structure self-assembles in acidic aqueous solution and is the most stable structure of polyoxometalate catalysts.

Thiophosphates are chemical compounds and anions with the general chemical formula PS
4−xO3−
x and related derivatives where organic groups are attached to one or more O or S. Thiophosphates feature tetrahedral phosphorus(V) centers.

Metal aquo complexes are coordination compounds containing metal ions with only water as a ligand. These complexes are the predominant species in aqueous solutions of many metal salts, such as metal nitrates, sulfates, and perchlorates. They have the general stoichiometry [M(H2O)n]z+. Their behavior underpins many aspects of environmental, biological, and industrial chemistry. This article focuses on complexes where water is the only ligand ("homoleptic aquo complexes"), but of course many complexes are known to consist of a mix of aquo and other ligands.

A metal ion in aqueous solution or aqua ion is a cation, dissolved in water, of chemical formula [M(H2O)n]z+. The solvation number, n, determined by a variety of experimental methods is 4 for Li+ and Be2+ and 6 for elements in periods 3 and 4 of the periodic table. Lanthanide and actinide aqua ions have a solvation number of 8 or 9. The strength of the bonds between the metal ion and water molecules in the primary solvation shell increases with the electrical charge, z, on the metal ion and decreases as its ionic radius, r, increases. Aqua ions are subject to hydrolysis. The logarithm of the first hydrolysis constant is proportional to z2/r for most aqua ions.

Evolution of metal ions in biological systems refers to the incorporation of metallic ions into living organisms and how it has changed over time. Metal ions have been associated with biological systems for billions of years, but only in the last century have scientists began to truly appreciate the scale of their influence. Major and minor metal ions have become aligned with living organisms through the interplay of biogeochemical weathering and metabolic pathways involving the products of that weathering. The associated complexes have evolved over time.

Compounds of nickel are chemical compounds containing the element nickel which is a member of the group 10 of the periodic table. Most compounds in the group have an oxidation state of +2. Nickel is classified as a transition metal with nickel(II) having much chemical behaviour in common with iron(II) and cobalt(II). Many salts of nickel(II) are isomorphous with salts of magnesium due to the ionic radii of the cations being almost the same. Nickel forms many coordination complexes. Nickel tetracarbonyl was the first pure metal carbonyl produced, and is unusual in its volatility. Metalloproteins containing nickel are found in biological systems.

Metal peroxide

Metal peroxides are metal-containing compounds with ionically- or covalently-bonded peroxide (O2−
2) groups. This large family of compounds can be divided into ionic and covalent peroxide. The first class mostly contains the peroxides of the alkali and alkaline earth metals whereas the covalent peroxides are represented by such compounds as hydrogen peroxide and peroxymonosulfuric acid (H2SO5). In contrast to the purely ionic character of alkali metal peroxides, peroxides of transition metals have a more covalent character.

References

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  15. ↑ IUPAC SC-Database
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