Nickel Compounds
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Nickel compounds are chemical compounds containing the element
nickel Nickel is a chemical element; it has symbol Ni and atomic number 28. It is a silvery-white lustrous metal with a slight golden tinge. Nickel is a hard and ductile transition metal. Pure nickel is chemically reactive, but large pieces are slo ...
which is a member of the group 10 of the
periodic table The periodic table, also known as the periodic table of the elements, is an ordered arrangement of the chemical elements into rows (" periods") and columns (" groups"). It is an icon of chemistry and is widely used in physics and other s ...
. Most compounds in the group have an
oxidation state In chemistry, the oxidation state, or oxidation number, is the hypothetical Electrical charge, charge of an atom if all of its Chemical bond, bonds to other atoms are fully Ionic bond, ionic. It describes the degree of oxidation (loss of electrons ...
of +2. Nickel is classified as a
transition metal In chemistry, a transition metal (or transition element) is a chemical element in the d-block of the periodic table (groups 3 to 12), though the elements of group 12 (and less often group 3) are sometimes excluded. The lanthanide and actinid ...
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 Magnesium is a chemical element; it has Symbol (chemistry), symbol Mg and atomic number 12. It is a shiny gray metal having a low density, low melting point and high chemical reactivity. Like the other alkaline earth metals (group 2 ...
due to the ionic radii of the cations being almost the same. Nickel forms many
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 ' ...
es. Nickel tetracarbonyl was the first pure metal carbonyl produced, and is unusual in its volatility.
Metalloprotein 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 (out of ~20,000) contain zinc-binding protein domains al ...
s containing nickel are found in biological systems. Nickel forms simple binary compounds with non metals including
halogens The halogens () are a group (periodic table), group in the periodic table consisting of six chemically related chemical element, elements: fluorine (F), chlorine (Cl), bromine (Br), iodine (I), and the radioactive elements astatine (At) and ten ...
, chalcogenides, and pnictides. Nickel ions can act as a cation in salts with many acids, including common
oxoacid An oxyacid, oxoacid, or ternary acid is an acid that contains oxygen. Specifically, it is a compound that contains hydrogen, oxygen, and at least one other element, with at least one hydrogen atom bonded to oxygen that can dissociate to produce ...
s. Salts of the hexaaqua ion (Ni2+) are especially well known. Many double salts containing nickel with another cation are known. There are organic acid salts. Nickel can be part of a negatively charged ion (anion) making what is called a nickellate. Numerous quaternary compounds (with four elements) of nickel have been studied for
superconductivity Superconductivity is a set of physical properties observed in superconductors: materials where Electrical resistance and conductance, electrical resistance vanishes and Magnetic field, magnetic fields are expelled from the material. Unlike an ord ...
properties, as nickel is adjacent to copper and iron in the periodic table can form compounds with the same structure as the
high-temperature superconductor High-temperature superconductivity (high-c or HTS) is superconductivity in materials with a critical temperature (the temperature below which the material behaves as a superconductor) above , the boiling point of liquid nitrogen. They are "high- ...
s that are known.


Colour

Most of the common
salts In chemistry, a salt or ionic compound is a chemical compound consisting of an assembly of positively charged ions ( cations) and negatively charged ions (anions), which results in a compound with no net electric charge (electrically neutral). ...
of nickel are green due to the presence of hexaaquanickel(II) ion, Ni(H2O)62+.


Geometry

Nickel atoms can connect to surrounding atoms or ligands in a variety of ways. Six coordinated nickel is the most common and is
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 ...
, but this can be distorted if ligands are not equivalent. For four coordinate nickel arrangements can be square planar, or
tetrahedral In geometry, a tetrahedron (: tetrahedra or tetrahedrons), also known as a triangular pyramid, is a polyhedron composed of four triangular Face (geometry), faces, six straight Edge (geometry), edges, and four vertex (geometry), vertices. The tet ...
. Five coordinated nickel is rarer.


Magnetism

Some nickel compounds are
ferromagnetic Ferromagnetism is a property of certain materials (such as iron) that results in a significant, observable magnetic permeability, and in many cases, a significant magnetic coercivity, allowing the material to form a permanent magnet. Ferromagne ...
at sufficiently low temperatures. In order to show magnetic properties the nickel atoms have to be close enough together in the solid structure.


Binary compounds

A binary compound of nickel contains one other element. Substances that contain only nickel atoms are not actually compounds. In a noble gas matrix, nickel can form dimers, a molecule with two nickel atoms: Ni2. Ni2 has a bonding energy of 2.07±0.01 eV. For Ni2+ the bond energy is around 3.3 eV. Nickel dimers and other clusters can also be formed in a gas and plasma phase by shooting a powerful laser at a nickel rod in cold helium gas.


Oxides

Nickel oxides include
Nickel(II) oxide Nickel(II) oxide is the chemical compound with the formula . It is the principal oxide of nickel. It is classified as a basic metal oxide. Several million kilograms are produced annually of varying quality, mainly as an intermediate in the product ...
and Nickel(III) oxide.


Hydroxides

Nickel hydroxides are used in nickel–cadmium and Nickel–metal hydride batteries. Nickel(II) hydroxide Ni(OH)2, the main hydroxide of nickel is coloured apple green. It is known as the mineral theophrastite. β-NiO(OH) is a black powder with nickel in the +3 oxidation state. It can be made by oxidising nickel nitrate in a cold alkaline solution with
bromine Bromine is a chemical element; it has chemical symbol, symbol Br and atomic number 35. It is a volatile red-brown liquid at room temperature that evaporates readily to form a similarly coloured vapour. Its properties are intermediate between th ...
. A mixed oxidation state hydroxide Ni3O2(OH)4 is made if oxidation happens in a hot alkaline solution. A Ni4+ hydroxide: nickel peroxide hydrate NiO2, can be made by oxidising with alkaline peroxide. It is black, and unstable and oxidises water.


Halides

Nickel(II) fluoride NiF2 is yellow, crystallising in the rutile structure and can form a trihydrate, NiF2·3H2O. A tetrahydrate also exists. Nickel(III) fluoride NiF3 and Nickel(IV) fluoride NiF4 also exist. Nickel chloride NiCl2 is yellow, crystallising in the cadmium chloride structure. It can form a hexahydrate, NiCl2·6H2O, a tetrahydrate NiCl2·4H2O over 29 °C and a dihydrate, NiCl2·2H2O over 64 °C. Ammine complexes like hexaamminenickel chloride also exist. Nickel bromide NiBr2 is yellow, also crystallising in the cadmium chloride structure. It can form a hexahydrate, NiBr2·6H2O. Crystallisation above 29° forms a trihydrate NiBr2·3H2O, and a dihydrate NiBr2·2H2O.Nicholls p1126-1127 Nonahydrate, NiBr2·9H2O can crystallise from water below 2 °C. Nickelous hexammine bromide Ni(NH3)6Br2is violet or blue. It is soluble in boiling aqueous
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 ...
, but is insoluble in cold. Diammine, monoammine, and dihydrazine nickel bromides also exist. With four bromide atoms, nickel(II) forms a series of salts called tetrabromonickelates. Nickel iodide NiI2 is black, also crystallising in the cadmium chloride structure. It can form a green hexahydrate, NiI2·6H2O. Nickel iodide has a brown diammine NiI2•2NH3 and a bluish-violet hexammine NiI2•6NH3.


Chalcogenides

By reacting nickel with
chalcogen The chalcogens (ore forming) ( ) are the chemical elements in group 16 of the periodic table. This group is also known as the oxygen family. Group 16 consists of the elements oxygen (O), sulfur (S), selenium (Se), tellurium (Te), and the rad ...
s,
nickel sulfide Nickel sulfide is any inorganic compound with the formula NixSy. These compounds range in color from bronze (Ni3S2) to black (NiS2). The nickel sulfide with simplest stoichiometry is NiS, also known as the mineral millerite. From the economic ...
, nickel selenide, and nickel telluride are formed. There are numerous sulfides: Ni1.5S, Ni17S18, Ni3S2 ( heazlewoodite), Ni3S4 ( polydymite), Ni9S8 ( godlevskite), NiS ( millerite) and two other NiS forms, NiS2 ( vaesite) in pyrite structure. Black nickel tetrasulfide NiS4 is formed from ammonium polysulfide and nickel in water solution. Mixed and double sulfides of nickel also exist. Nickel with
selenium Selenium is a chemical element; it has symbol (chemistry), symbol Se and atomic number 34. It has various physical appearances, including a brick-red powder, a vitreous black solid, and a grey metallic-looking form. It seldom occurs in this elem ...
forms several compounds Ni1−xSe 0≤x≤0.15, Ni2Se3, NiSe2 also known as a mineral penroseite. Nickel forms two different polonides by heating nickel and
polonium Polonium is a chemical element; it has symbol Po and atomic number 84. A rare and highly radioactive metal (although sometimes classified as a metalloid) with no stable isotopes, polonium is a chalcogen and chemically similar to selenium and tel ...
together: NiPo and NiPo2.


Pnictides

Non-stoichiometric Non-stoichiometric compounds are chemical compounds, almost always solid inorganic compounds, having chemical element, elemental composition whose proportions cannot be represented by a ratio of small natural numbers (i.e. an empirical formula); ...
compounds of nickel with
phosphorus Phosphorus is a chemical element; it has Chemical symbol, symbol P and atomic number 15. All elemental forms of phosphorus are highly Reactivity (chemistry), reactive and are therefore never found in nature. They can nevertheless be prepared ar ...
,
arsenic Arsenic is a chemical element; it has Symbol (chemistry), symbol As and atomic number 33. It is a metalloid and one of the pnictogens, and therefore shares many properties with its group 15 neighbors phosphorus and antimony. Arsenic is not ...
and
antimony Antimony is a chemical element; it has chemical symbol, symbol Sb () and atomic number 51. A lustrous grey metal or metalloid, it is found in nature mainly as the sulfide mineral stibnite (). Antimony compounds have been known since ancient t ...
exist, and some are found in nature. One interstitial
nitride In chemistry, a nitride is a chemical compound of nitrogen. Nitrides can be inorganic or organic, ionic or covalent. The nitride anion, N3−, is very elusive but compounds of nitride are numerous, although rarely naturally occurring. Some nitr ...
has formula Ni3N (hexagonal P6322, Z = 2, a = 4.6224 Å and c = 4.3059 Å). In a
solid nitrogen Solid nitrogen is a number of solid forms of the element nitrogen, first observed in 1884. Solid nitrogen is mainly the subject of academic research, but low-temperature, low-pressure solid nitrogen is a substantial component of bodies in the ou ...
matrix, nickel atoms combine with nitrogen molecules to yield Ni(N2)4. Nickel phosphide Ni2P has density 7.33 and melts at 1100 °C. The mineral Nickelskutterudite has formula NiAs2-3,
nickeline Nickeline or niccolite is the mineral form of nickel arsenide. The naturally-occurring mineral contains roughly 43.9% nickel and 56.1% arsenic by mass, but composition of the mineral may vary slightly. Small quantities of sulfur, iron and cobalt ...
has formula NiAs and breithauptite has formula NiSb. NiAs melts at 967° and has density 7.77. NiSb melts at 1174°. It has the highest density of a nickel compound at 8.74 g/cm3. NiAsS gersdorffite, and NiSbS ullmannite, NiAsSe Jolliffeite are pnictide/chalcogenide compounds that occur as minerals.


Other

Nickel also forms
carbide In chemistry, a carbide usually describes a compound composed of carbon and a metal. In metallurgy, carbiding or carburizing is the process for producing carbide coatings on a metal piece. Interstitial / Metallic carbides The carbides of th ...
s and borides. Nickel borides include forms Ni2B (a green/black solid), NiB, Ni3B, ''o''-Ni4B3 and ''m''-Ni4B3. Nickel hydride NiH is only stable under
high pressure In science and engineering the study of high pressure examines its effects on materials and the design and construction of devices, such as a diamond anvil cell, which can create high pressure. ''High pressure'' usually means pressures of thousan ...
s of
hydrogen Hydrogen is a chemical element; it has chemical symbol, symbol H and atomic number 1. It is the lightest and abundance of the chemical elements, most abundant chemical element in the universe, constituting about 75% of all baryon, normal matter ...
. Nickel silicides include Ni3Si, Ni31Si12, Ni2Si, Ni3Si2, NiSi and NiSi2. Nickel silicides are used in
microelectronics Microelectronics is a subfield of electronics. As the name suggests, microelectronics relates to the study and manufacture (or microfabrication) of very small electronic designs and components. Usually, but not always, this means micrometre ...
.


Diatomic molecules

Hot nickel vapour reacting with other atoms in the gas phase can produce molecules consisting of two atoms. These can be studied by their
emission spectrum The emission spectrum of a chemical element or chemical compound is the Spectrum (physical sciences), spectrum of frequencies of electromagnetic radiation emitted due to electrons making a atomic electron transition, transition from a high energ ...
. The nickel monohalides are well studied.


Alloys

Compounds of nickel with other metals can be called
alloy An alloy is a mixture of chemical elements of which in most cases at least one is a metal, metallic element, although it is also sometimes used for mixtures of elements; herein only metallic alloys are described. Metallic alloys often have prop ...
s. The substances with fixed composition include nickel aluminide (NiAl) melting at 1638° with hexagonal structure. NiY, NiY3, Ni3Y, Ni4Y, NiGd3, BaNi2Ge2 changes structure from orthorhombic to tetragonal around 480 °C. This is a ternary intermetallic compound. Others include BaNiSn3 and the superconductors SrNi2Ge2, SrNi2P2, SrNi2As2, BaNi2P2, BaNi2As2.


Simple salts


Oxo acid salts

Important nickel oxo acid salts include nickel(II) sulfate can crystallise with six water molecules yielding Retgersite or with seven making Morenosite which is isomorphic to Epsom salts. These contain the hexaquanickel(II) ion. There is also an anhydrous form, a dihydrate and a tetrahydrate, the last two crystallised from
sulfuric acid Sulfuric acid (American spelling and the preferred IUPAC name) or sulphuric acid (English in the Commonwealth of Nations, Commonwealth spelling), known in antiquity as oil of vitriol, is a mineral acid composed of the elements sulfur, oxygen, ...
. The hexahydrate has two forms, a blue tetragonal form, and a green monoclinic form, with a transition temperature around 53 °C. The heptahydrate crystallises from water below 31.5 above this blue hexhydrate forms, and above 53.3 the green form. Heating nickel sulfate dehydrates it, and then 700° it loses sulfur trioxide, sulfur dioxide and oxygen. Other important nickel compounds in this class are nickel carbonate, nickel nitrate, and nickel phosphate


Fluoro acid salts

Nickel tetrafluoroborate, Ni(BF4)2 is very soluble in water, alcohol and acetonitrile. It is prepared by dissolving nickel carbonate in tetrafluoroboric acid. Nickel tetrafluoroberyllate NiBeF4•''x''H2O, can be hydrated with six or seven water molecules. Both nickel hexafluorostannate \ce and nickel fluorosilicate \ce crystallise in the trigonal system. Nickel hexafluorogermanate NiGeF6 has a rosy-tan colour and a hexagonal crystal with a = 5.241 Å unit cell volume is 92.9 Å3. It is formed in the reaction with GeF4 and K2NiF6. Nickel fuorotitanate \ce crystallises in hexagonal green crystals. It can be made by dissolving nickel carbonate, and titanium dioxide in hydrofluoric acid. The crystal dimensions are a = 9.54, c = 9.91 density = 2.09 (measure 2.03). Ni(AsF6)2, Ni(SbF6)2, Ni(BiF6)2 are made by reacting the hexafluoro acid with NiF2 in
hydrofluoric acid Hydrofluoric acid is a solution of hydrogen fluoride (HF) in water. Solutions of HF are colorless, acidic and highly corrosive. A common concentration is 49% (48–52%) but there are also stronger solutions (e.g. 70%) and pure HF has a boiling p ...
. They all have hexagonal crystal structure, resembling the similar salts of the other first row transition metals. For Ni(AsF6)2 a = 4.98, c = 26.59, and V = 571, formula weight Z=3. Ni(SbF6)2 is yellow with a = 5.16Å, c = 27.90Å Z = 3. The structure resembles LiSbF6, but with every second metal along the c axis missing. Others include the green fluorohafnate NiHfF6, and Ni2HfF8, NiZrF6


Chloroacid salts

Nickel tetrachloroiodate Ni(ICl4)2 can be made by reacting iodine with nickel chloride and chlorine gas. It consists of green needles.


Nitrogen anion salts

Nickel cyanide tetrahydrate Ni(CN)2 is insoluble in water, but dissolves in aqueous ammonia. It forms double salts with interesting structures. Nickel azide Ni(N3)2 is a sensitive explosive. It can be made by treating nickel carbonate with hydrazoic acid. Acetone causes the precipitation of the hydrous solid salt, which is green. At 490K it slowly decomposes to nitrogen and nickel metal powder, losing a half of the nitrogen in four hours. Nickel azide is complexed by one azo group when dissolved in water, but in other solvents, the nickel atom can have up to four azo groups attached. Nickel azide forms a dihydrate: Ni(N3)2 and a basic salt called nickel hydroxy azide Ni(OH)N3. Nickel amide, Ni(NH2)2 is a deep red compound that contains Ni6 clusters surrounded by 12 NH2 groups. Nickel amide also forms a series of double salts. Other homoleptic nickel amides derived by substituting the hydrogen atoms are Ni (C6H5)2sub>2 (diphenyl) and boryl amides Ni BMes2Messub>2 and Ni BMes2C6H5sub>2.


Organic acid salts

Nickel forms many known salts with organic acids. In many of these the ionised organic acid acts as a ligand.


Double salts

Nickel is one of the metals that can form Tutton's salts. The singly charged ion can be any of the full range of potassium, rubidium, cesium, ammonium (NH4), or thallium. As a mineral the ammonium nickel salt, (NH4)2Ni(SO4)2, can be called nickelboussingaultite. With sodium, the double sulfate is nickelblödite Na2Ni(SO4)2 from the blödite family. Nickel can be substituted by other divalent metals of similar sized to make mixtures that crystallise in the same form. Nickel forms double salts with Tutton's salt structure with tetrafluoroberyllate with the range of cations of ammonia, potassium, rubidium, cesium, and thallium. Anhydrous salts of the formula M2Ni2(SO4)3, which can be termed metal nickel trisulfates, belong to the family of langbeinites. The known salts include (NH4)2Ni2(SO4)3, K2Ni2(SO4)3 and Rb2Ni2(SO4)3, and those of Tl and Cs are predicted to exist. Some minerals are double salts, for example Nickelzippeite Ni2(UO2)6(SO4)3(OH)10 · 16H2O which is isomorphic to cobaltzippeite, magnesiozippeite and zinczippeite, part of the zippeite group. Double hydrides of nickel exist, such as Mg2NiH4.


Ternary chalcogenides

Nickel forms a series of double nickel oxides with other elements, which may be termed "nickelates". There are also many well defined double compounds with sulfur, selenium and tellurium.


Ternary pnictides

Ternary pnictides that contain nickel are metallic and include MgNi2Bi4, SrNi2P2, SrNi2As2, BaNi2P2, and BaNi2As2.


Ternary halides

Nickel can form anions and salts with halogens including the hexafluoronickelates, and tetrafluoronickelates, tetrachloronickelates, tetrabromonickelates and tetraiodonickelates. The subiodide Bi12Ni4I3 is also known.


Polyoxometallates

Nickel can enter into metal oxygen clusters with other high oxidation state elements to form
polyoxometalate In chemistry, a polyoxometalate (abbreviated POM) is a polyatomic ion, usually an anion, that consists of three or more transition metal oxyanions linked together by shared oxygen atoms to form closed 3-dimensional frameworks. The metal atoms are ...
s. These may stabilize higher oxidation states of nickel, or show catalytic properties. Nonamolybdonickelate(IV), iMo9O32sup>6− can oxidize aromatic hydrocarbons to alcohols. There is a dark brown heptamolybdonickelate(IV) potassium salt, K2H8NiMo7O28·6H2O. 13-Vanadonickelate(IV) compounds such as K7NiV13O38 with black octahedral crystals exist. It can be made from isopolyvanadate, with nickel(II) oxidised by peroxydisulfate at a pH around 4. Nickel(IV) heteropolyniobates such as the dark maroon Na12NiNb12O38 are also known. An alternate orange red hydrate perhaps with 44 water molecules also exists. With nickel-II (tetramethylammonium)6[H3NiNb9O28 forms a green salt that is very soluble in water, but hardly soluble in ethanol. H43K14Na6Nb32 Ni10O183 is a nickel-cation-bridged polyoxoniobate which crystallizes in the monoclinic system with cell dimensions a=15.140 b=24.824 c=25.190 Å and β=103.469 and two formulas per unit cell. Na8Li12[Ni2(P2W15O56)2] forms a sandwich structure, and Na4Li5[Ni3(OH)3(H2O)3P2W16O59] is a Wells-Dawson polyoxometalate.


Acidic salts

Nickel hydrofluoride, H5NiF7·6H2O is made by using excess hydrofluoric acid solution on nickel carbonate. It is deep green.


Basic salts

Nickel oxyfluoride Ni4F4O(OH)2 is green. Nickelous enneaoxydiiodide 9NiO•Nil2 forms when solutions of nickel iodide are exposed to air and evaporated.


Complexes

Simple complexes of nickel include hexaquonickel(II), yellow
tetracyanonickelate The cyanonickelates are a class of chemical compound containing anions consisting of nickel atoms, and cyanide groups. The most important of these are the tetracyanonickelates containing four cyanide groups per nickel. The tetracyanonickelates c ...
i(CN)4sup>2−, red pentacyanonickelate i(CN)5sup>3− only found in solution, i(SCN)4sup>2− and i(SCN)6sup>4−. Halo- complexes include iCl4sup>2−, iF4sup>2−, iF6sup>4−, iCl2(H2O)4 i(NH3)4(H2O)2sup>2+, i(NH3)6sup>2+, i(en)3)sup>2+. Some complexes have fivefold coordination. N H2CH2NMe2 (tris(N,N-dimethyl-2-aminoethyl)amine); P(o-C6H4SMe)3; P(CH2CH2CH2AsMe2)3. Other ligands for octahedral coordination include PPh3, PPh2Me and
thiourea Thiourea () is an organosulfur compound with the formula and the structure . It is structurally similar to urea (), with the oxygen atom replaced by sulfur atom (as implied by the '' thio-'' prefix). The properties of urea and thiourea differ s ...
. Nickel tetrahedral complexes are often bright blue and 20 times or more intensely coloured than the octahedral complexes. The ligands can include selections of neutral
amine In chemistry, amines (, ) are organic compounds that contain carbon-nitrogen bonds. Amines are formed when one or more hydrogen atoms in ammonia are replaced by alkyl or aryl groups. The nitrogen atom in an amine possesses a lone pair of elec ...
s, arsines, arsine oxides,
phosphine Phosphine (IUPAC name: phosphane) is a colorless, flammable, highly toxic compound with the chemical formula , classed as a pnictogen hydride. Pure phosphine is odorless, but technical grade samples have a highly unpleasant odor like rotting ...
s or
phosphine oxide Phosphine oxide is the inorganic compound with the formula H3PO. Although stable as a dilute gas, liquid or solid samples are unstable. Unlike many other compounds of the type POxHy, H3PO is rarely discussed and is not even mentioned in major so ...
s and halogens. Several nickel atoms can cluster together in a compound with other elements to produce nickel cluster complexes. One example where nickel atoms form a square pyramid is a nickel hydride cluster complexed by triphenyl phosphine ligands and bonding a hydrogen atom on each edge. Another example has a square planar Ni4H4 shape in its core. Nickel bis(dimethylglyoximate), an insoluble red solid is important for
gravimetric analysis Gravimetric analysis describes a set of methods used in analytical chemistry for the quantitative determination of an analyte (the ion being analyzed) based on its mass. The principle of this type of analysis is that once an ion's mass has been ...
.


Biological molecules

Cofactor F430 contains nickel in a tetrapyrrole derivative, and is used in the production of methane. Some
hydrogenase A hydrogenase is an enzyme that Catalysis, catalyses the reversible Redox, oxidation of molecular hydrogen (H2), as shown below: Hydrogen oxidation () is coupled to the reduction of electron acceptors such as oxygen, nitrate, Ferric, ferric i ...
enzymes contain a nickel-iron cluster as an active site in which the nickel atom is held in place by
cysteine Cysteine (; symbol Cys or C) is a semiessential proteinogenic amino acid with the chemical formula, formula . The thiol side chain in cysteine enables the formation of Disulfide, disulfide bonds, and often participates in enzymatic reactions as ...
or
selenocysteine Selenocysteine (symbol Sec or U, in older publications also as Se-Cys) is the 21st proteinogenic amino acid. Selenoproteins contain selenocysteine residues. Selenocysteine is an analogue of the more common cysteine with selenium in place of the ...
. Plant
urease Ureases (), functionally, belong to the superfamily of amidohydrolases and phosphotriesterases. Ureases are found in numerous Bacteria, Archaea, fungi, algae, plants, and some invertebrates. Ureases are nickel-containing metalloenzymes of high ...
s contain a bis-μ-hydroxo dimeric nickel cluster. CO-methylating acetyl-CoA synthase contains two active nickel atoms, one is held in a square planar coordination by two cysteine and two amide groups, and the other nickel is held by three sulfur atoms. It is used to catalyse the reduction of carbon monoxide to
acetyl-CoA Acetyl-CoA (acetyl coenzyme A) is a molecule that participates in many biochemical reactions in protein, carbohydrate and lipid metabolism. Its main function is to deliver the acetyl group to the citric acid cycle (Krebs cycle) to be oxidation, o ...
. Nickel superoxide dismutase (or Ni-SOD) from ''
Streptomyces ''Streptomyces'', from στρεπτός (''streptós''), meaning "twisted", and μύκης (''múkés''), meaning "fungus", is the largest genus of Actinomycetota, and the type genus of the family Streptomycetaceae. Over 700 species of ''St ...
'' contains six nickel atoms. The nickel holding is done by a "nickel binding hook" which as the amino acid pattern H2N-His-Cys-X-X-Pro-Cys-Gly-X-Tyr-rest of protein, where the bold bits are ligands for the nickel atom. Nickel transporter proteins exist to move nickel atoms in the cell. in '' E. coli'' these are termed ''Nik''A, ''Nik''B, ''Nik''C, ''Nik''D, ''Nik''E. In order to come through a cell membrane a nickel permease protein is used. In '' Alcaligenes eutrophus'' the gene for this is ''hox''N.


Organometallics

Well known nickel organometalic (or organonickel) compounds include Nickelocene, bis(cyclooctadiene)nickel(0) and nickel tetracarbonyl. Nickel tetracarbonyl was the first discovered organonickel compound. It was discovered that carbon monoxide corroded a nickel reaction chamber valve. And then that the gas coloured a bunsen burner flame green, and then that a nickel mirror condensed from heating the gas. The Mond process was thus inspired to purify nickel. The nickel tetracarbonyl molecule is tetrahedral, with a bond length for nickel to carbon of 1.82 Å. Nickel tetracarbonyl easily starts breaking apart over 36° forming Ni(CO)3, Ni(CO)2, and Ni. Ni(CO) and NiC appear in mass spectroscopy of nickel carbonyl. There are several nickel carbonyl cluster anions formed by reduction from nickel carbonyl. These are i2(CO)5sup>2−, dark red i3(CO)8sup>2−, i4(CO)9sup>2−, i5(CO)9sup>2−, i6(CO)12sup>2−. Salts such as Cd i4(CO)9and Li2 i3(CO)85acetone can be crystallised. Mixed cluster carbonyl anions like r2Ni3(CO)16sup>2−, o2Ni3(CO)16sup>2− and 2Ni3(CO)16sup>2− o4(CO)14sup>2− can form salts with bulky cations like tetraethylammonium. The brown iCo3(CO)11sup>− changes to red i2Co4(CO)14sup>2−. With oxygen or air the explosive Ni(CO)3O2 can be formed from nickel carbonyl. Yet other ligands can substitute for carbon monoxide in nickel carbonyl. These lewis base ligands include triphenylphosphine, triphenoxyphosphine, trimethoxyphosphine, tributylphosphine, triethoxyphosphine, triethylisonitrolphosphine, triphenylarsine, and triphenylstibine. Nickel forms dark blue planar complexes with 1,2-Diimino-3,5-cyclohexadiene or bisacetylbisaniline C6H5N-C(CH3)=)2sub>2Ni. Another planar bis compound of nickel is formed with phenylazothioformamide C6H5N=NC(S)NR2, and dithizone C6H5N=NC(S)NHNHC6H5. tetrasulfur tetranitride when reduced with nickel carbonyl makes Ni 2S2Hsub>2 also coloured dark violet. One nickellabenzene is known where nickel substitutes for carbon in benzene. At nickel the plane of the molecule is bent, however the connection to the ring has aromatic character. A hexavalent nickel complex, Ni(BeCp)6, has been synthesized, and aromaticity has also been calculated to contribute to its stability.


Alkoxy compounds

Nickel ''tert''-butoxide Ni C(CH3)3sub>2 is coloured violet. It is formed in the reaction of di-''tert''-butylperoxide with nickel carbonyl. Nickel dimethoxide is coloured green. There are also nickel chloride methoxides with formulae: NiClOMe, Ni3Cl2(OMe)4 and Ni3Cl(OMe)5 in which Nickel and oxygen appear to form a cubane-type cluster. Other alkoxy compounds known for nickel include nickel dipropoxide, nickel di-isopropoxide, nickel ''tert''-amyloxide, and nickel di-''tert''-hexanoxide. These can be formed by crystallising nickel chloride from the corresponding alcohol, which forms an adduct. This is then heated with a base. Nickel(II) alkoxy compounds are polymeric and non-volatile. Ziegler catalysis uses nickel as a catalyst. In addition it uses diethylaluminum ethoxide, phenylacetylene and
triethylaluminium Triethylaluminium is one of the simplest examples of an organoaluminium compound. Despite its name the compound has the formula Al2( C2H5)6 (abbreviated as Al2Et6 or TEA). This colorless liquid is pyrophoric. It is an industrially important comp ...
It converts
ethylene Ethylene (IUPAC name: ethene) is a hydrocarbon which has the formula or . It is a colourless, flammable gas with a faint "sweet and musky" odour when pure. It is the simplest alkene (a hydrocarbon with carbon–carbon bond, carbon–carbon doub ...
into
1-butene 1-Butene (IUPAC name: But-1-ene, also known as 1-butylene) is the organic compound with the formula CH3CH2CH=CH2. It is a colorless gas, but easily condensed to give a colorless liquid. It is classified as a linear alpha-olefin (terminal alkene). ...
. It can dimerise
propylene Propylene, also known as propene, is an unsaturated organic compound with the chemical formula . It has one double bond, and is the second simplest member of the alkene class of hydrocarbons. It is a colorless gas with a faint petroleum-like o ...
. The catalyst, when combined with optically active phosphines, can produce optically active dimers. An intermediate formed is tris(ethylene)nickel.(CH2=CH2)3Ni in which the ethylene molecules connect to the nickel atom side on. Homoletptic bimetallic alkoxides have two different metals, and the same alkoxy group. They include Ni μ−OMe)3AlOMesub>2, Ni l(OBut)4sub>2 (nickel tetra-''tert''-butoxyaluminate) and Ni l(OPri)4sub>2. (nickel tetra-isopropoxyaluminate a pink liquid) Potassium hexaisoproxynoibate and tantalate can react with nickel chloride to make Ni b(OPri)6sub>2 and Ni a(OPri)6sub>2. Ni r2(OPri)9sub>2 The bimetallic alkoxides are volatile and can dissolve in organic solvents. A trimetallic one exists r2(OPri)9i l(OPri)4 NiGe(OBut)8], NiSn(OBut)8] and NiPb(OBut)8] are tricyclic. i2(μ3−OEt)2(μ−OEt)8Sb4(OEt)6 Heteroleptic bitmetallic ethoxides have more than one variety of alkoxy group, e.g. Ni μ−OPri)(μ−OBut)Al(OBut)2sub>2 which is a purple solid. Oxoalkoxides contain extra oxygen in addition to the alcohol. With only nickel, none are known, but with antimony an octanuclear molecule exists i5Sb3(μ4−O)2(μ3−OEt)3(−OEt)9(OEt)3(EtOH)4


Aryloxy compounds

There are many nickel compounds with the formula template Ni(OAr)XL2 and Ni(OAr)2L2. L is a ligand with phosphorus or nitrogen atoms. OAr is a phenol group or O- attached to an aromatic ring. Often an extra molecule of the phenol is hydrogen bonded to the oxygen attached to nickel.


μ-bonded molecules

Others include
cyclododecatriene Cyclododecatrienes are cyclic trienes with the formula C12H18. Four isomers are known for 1,5,9-cyclododecatriene. The ''trans'',''trans'',''cis''-isomer is a precursor in the production of nylon-12. : Production The ''trans'',''trans'',''cis'' ...
nickel and ''t''-Ni(cdt).


Sulfur rings

Nickel bis-dithiobenzoate can form a violet coloured sodium salt. Two bisperfluoromethyl-l,2-dithietene molecules react with nickel carbonyl to make a double ring compound with nickel linked to four sulfur atoms. This contains four trifluoromethyl groups and is dark purple. Instead of this methyl or phenyl can substitute. These can be made by substituted acetylenes with sulfur on nickel carbonyl, or on nickel sulfide. Bis-diphenyldithiene nickel has a planar structure


Nickel chalcogen cluster compound

A hexameric compound i(SR)2sub>6 is produced in the reaction of nickel carbonyl with dialkyl sulfides (RSR). Nickel can be part of a cubane-type cluster with iron and
chalcogen The chalcogens (ore forming) ( ) are the chemical elements in group 16 of the periodic table. This group is also known as the oxygen family. Group 16 consists of the elements oxygen (O), sulfur (S), selenium (Se), tellurium (Te), and the rad ...
s. The metal atoms are arranged in a tetrahedron shape, with the sulfur or selenium making up another tetrahedron that combines to make a cube. For example, the iFe3S4(PPh3)(SEt)3sup>2− is a dianion that has a tetraethyl ammonium salt. Similar ion clusters are iFe3Se4(PPh3)(SEt)3sup>2− and iFe3Se4(SEt)4sup>3−. In the natural world cube shaped metal sulfur clusters can have sulfur atoms that are part of
cysteine Cysteine (; symbol Cys or C) is a semiessential proteinogenic amino acid with the chemical formula, formula . The thiol side chain in cysteine enables the formation of Disulfide, disulfide bonds, and often participates in enzymatic reactions as ...
. i4Se23sup>4− has a cube with Ni4Se4 at its core, and then the nickel atoms are bridge across the cube faces by five Se3 chains and one Se4 chain. It is formed as a tetraethylammonium salt, from Li2Se, Se, NEt4Cl and nickel dixanthate in
dimethylformamide Dimethylformamide, DMF is an organic compound with the chemical formula . Its structure is . Commonly abbreviated as DMF (although this initialism is sometimes used for 2,5-dimethylfuran, dimethylfuran, or dimethyl fumarate), this colourless liqui ...
as a solvent. This reaction also produces (NEt4)2Ni(Se4)2.


Nitrosyl compounds

When liquid nickel carbonyl is dissolved in liquid hydrogen chloride, it can react with nitrosyl chloride to form a dimer Ni(NOCl)2. This then decomposes to Ni(NO)Cl2, which is polymeric. Nickel carbonyl reacting with
nitric oxide Nitric oxide (nitrogen oxide, nitrogen monooxide, 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 den ...
yields blue coloured mononitrosyl nickel NiNO. With cyclohexane as well, pale blue Ni(NO2)NO is produced with nitrous oxide as a side product. With cyclopentadiene as well, π-C5H5NiNO is produced.


See also

* :Nickel compounds * Nickel(IV) organometallic complex


References


Sources

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