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Nickel(II) chloride

Nickel(II) chloride

Overview
Nickel chloride (or just nickel chloride), is the chemical compound
Chemical compound
A chemical compound is a pure chemical substance consisting of two or more different chemical elements that can be separated into simpler substances by chemical reactions. Chemical compounds have a unique and defined chemical structure; they consist of a fixed ratio of atoms that are held together...

 NiCl2. The anhydrous
Anhydrous
As a general term, a substance is said to be anhydrous if it contains no water. The way of achieving the anhydrous form differs from one substance to another...

 salt is yellow, but the more familiar hydrate
Water of crystallization
In crystallography, water of crystallization or water of hydration or crystallization water is water that occurs in crystals. Water of crystallization is necessary for the maintenance of crystalline properties, but capable of being removed by sufficient heat...

 NiCl2·6H2O is green. It is very rarely found in nature as mineral nickelbischofite. A dihydrate is also known. In general nickel(II) chloride, in various forms, is the most important source of nickel for chemical synthesis. Nickel
Nickel
Nickel is a chemical element with the chemical symbol Ni and atomic number 28. It is a silvery-white lustrous metal with a slight golden tinge. Nickel belongs to the transition metals and is hard and ductile...

 salts are carcinogen
Carcinogen
A carcinogen is any substance, radionuclide, or radiation that is an agent directly involved in causing cancer. This may be due to the ability to damage the genome or to the disruption of cellular metabolic processes...

ic.
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Encyclopedia
Nickel chloride (or just nickel chloride), is the chemical compound
Chemical compound
A chemical compound is a pure chemical substance consisting of two or more different chemical elements that can be separated into simpler substances by chemical reactions. Chemical compounds have a unique and defined chemical structure; they consist of a fixed ratio of atoms that are held together...

 NiCl2. The anhydrous
Anhydrous
As a general term, a substance is said to be anhydrous if it contains no water. The way of achieving the anhydrous form differs from one substance to another...

 salt is yellow, but the more familiar hydrate
Water of crystallization
In crystallography, water of crystallization or water of hydration or crystallization water is water that occurs in crystals. Water of crystallization is necessary for the maintenance of crystalline properties, but capable of being removed by sufficient heat...

 NiCl2·6H2O is green. It is very rarely found in nature as mineral nickelbischofite. A dihydrate is also known. In general nickel(II) chloride, in various forms, is the most important source of nickel for chemical synthesis. Nickel
Nickel
Nickel is a chemical element with the chemical symbol Ni and atomic number 28. It is a silvery-white lustrous metal with a slight golden tinge. Nickel belongs to the transition metals and is hard and ductile...

 salts are carcinogen
Carcinogen
A carcinogen is any substance, radionuclide, or radiation that is an agent directly involved in causing cancer. This may be due to the ability to damage the genome or to the disruption of cellular metabolic processes...

ic. They are also deliquescent, absorbing moisture from the air to form a solution.

Production and syntheses


Probably the largest scale production of nickel chloride involves the extraction with hydrochloric acid of nickel matte
Matte (metallurgy)
Matte is a term used in the field of pyrometallurgy given to the molten metal sulfide phases typically formed during smelting of copper, nickel, and other base metals. Typically, a matte is the phase in which the principal metal being extracted is recovered prior to a final reduction process to...

 and residues obtained from roasting refining nickel-containing ores.

NiCl2·6H2O is rarely prepared in the laboratory because it is inexpensive and has a long shelf-life. The hydrate can be converted to the anhydrous form upon heating in thionyl chloride
Thionyl chloride
Thionyl chloride is an inorganic compound with the formula SOCl2. It is a reactive chemical reagent used in chlorination reactions. It is a colorless, distillable liquid at room temperature and pressure that decomposes above 140 °C. Thionyl chloride is sometimes confused with sulfuryl...

 or by heating under a stream of HCl gas. Simply heating the hydrates does not afford the anhydrous dichloride.
NiCl2·6H2O + 6 SOCl2 → NiCl2 + 6 SO2 + 12 HCl
Hydrogen chloride
The compound hydrogen chloride has the formula HCl. At room temperature, it is a colorless gas, which forms white fumes of hydrochloric acid upon contact with atmospheric humidity. Hydrogen chloride gas and hydrochloric acid are important in technology and industry...


The dehydration is accompanied by a color change from green to yellow.

Structure and properties


NiCl2 adopts the CdCl2 structure. In this motif, each Ni2+ center is coordinated to six Cl- centers, and each chloride is bonded to three Ni(II) centers. In NiCl2 the Ni-Cl bonds have “ionic character”. Yellow NiBr2 and black NiI2 adopt similar structures, but with a different packing of the halides, adopting the CdI2 motif.

In contrast, NiCl2·6H2O consists of separated trans-[NiCl2(H2O)4] molecules linked more weakly to adjacent water molecules. Note that only four of the six water molecules in the formula are bound to the nickel, and the remaining two are water of crystallisation. Cobalt(II) chloride
Cobalt(II) chloride
Cobalt chloride is an inorganic compound of cobalt and chloride, with the formula CoCl2. It is usually supplied as the hexahydrate CoCl2·6H2O, which is one of the most commonly used cobalt compounds in the laboratory. The hexahydrate is deep purple in color, whereas the anhydrous form is sky blue...

 hexahydrate has a similar structure.

Many nickel(II) compounds are paramagnetic
Paramagnetism
Paramagnetism is a form of magnetism whereby the paramagnetic material is only attracted when in the presence of an externally applied magnetic field. In contrast with this, diamagnetic materials are repulsive when placed in a magnetic field...

, due to the presence of two unpaired electrons on each metal center. Square planar nickel complexes are, however, diamagnetic
Diamagnetism
Diamagnetism is the property of an object which causes it to create a magnetic field in opposition to an externally applied magnetic field, thus causing a repulsive effect. Specifically, an external magnetic field alters the orbital velocity of electrons around their nuclei, thus changing the...

.

Nickel(II) chloride solutions are acidic, with a pH of around 4 due to the hydrolysis of the Ni2+ ion.

Coordination chemistry



Most of the reactions ascribed to “nickel chloride” involve the hexahydrate, although specialized reactions require the anhydrous form.

Reactions starting from NiCl2·6H2O can be used to form a variety of nickel coordination
Complex (chemistry)
In chemistry, a coordination complex or metal complex, is an atom or ion , bonded to a surrounding array of molecules or anions, that are in turn known as ligands or complexing agents...

 complexes because the H2O ligands are rapidly displaced by ammonia
Ammonia
Ammonia is a compound of nitrogen and hydrogen with the formula . It is a colourless gas with a characteristic pungent odour. Ammonia contributes significantly to the nutritional needs of terrestrial organisms by serving as a precursor to food and fertilizers. Ammonia, either directly or...

, amine
Amine
Amines are organic compounds and functional groups that contain a basic nitrogen atom with a lone pair. Amines are derivatives of ammonia, wherein one or more hydrogen atoms have been replaced by a substituent such as an alkyl or aryl group. Important amines include amino acids, biogenic amines,...

s, thioether
Thioether
A thioether is a functional group in organosulfur chemistry with the connectivity C-S-C as shown on right. Like many other sulfur-containing compounds, volatile thioethers have foul odors. A thioether is similar to an ether except that it contains a sulfur atom in place of the oxygen...

s, thiolates, and organophosphine
Phosphine
Phosphine is the compound with the chemical formula PH3. It is a colorless, flammable, toxic gas. Pure phosphine is odourless, but technical grade samples have a highly unpleasant odor like garlic or rotting fish, due to the presence of substituted phosphine and diphosphine...

s. In some derivatives, the chloride remains within the coordination sphere
Coordination sphere
In coordination chemistry, the coordination sphere refers to a central atom or ion and an array of molecules or anions, the ligands, around.Molecules that are attached noncovalently to the ligands are called the second coordination sphere....

, whereas chloride is displaced with highly basic ligands. Illustrative complexes include:
Complex Color Magnetism Geometry
[Ni(NH3)6]Cl2 violet paramagnetic octahedral
NiCl2(dppe) orange diamagnetic square planar
[Ni(CN
Cyanide
A cyanide is a chemical compound that contains the cyano group, -C≡N, which consists of a carbon atom triple-bonded to a nitrogen atom. Cyanides most commonly refer to salts of the anion CN−. Most cyanides are highly toxic....

)4]2-
colorless diamagnetic square planar
[NiCl4]2- Yellowish-Brown paramagnetic tetrahedral


Some nickel chloride complexes exist as an equilibrium mixture of two geometries; these examples are some of the most dramatic illustrations of structural isomerism for a given coordination number
Coordination number
In chemistry and crystallography, the coordination number of a central atom in a molecule or crystal is the number of its nearest neighbours. This number is determined somewhat differently for molecules and for crystals....

. For example, NiCl2(PPh3)2, containing four-coordinate Ni(II), exists in solution as a mixture of both the diamagnetic square planar and the paramagnetic tetrahedral isomers. Square planar complexes of nickel can often form five-coordinate adducts.

NiCl2 is the precursor to acetylacetonate
Acetylacetone
Acetylacetone is an organic compound that famously exists in two tautomeric forms that rapidly interconvert. The less stable tautomer is a diketone formally named pentane-2,4-dione. The more common tautomer is the enol form. The pair of tautomers rapidly interconvert and are treated as a single...

 complexes Ni(acac)2(H2O)2 and the benzene-soluble (Ni(acac)2)3, which is a precursor to Ni(1,5-cyclooctadiene
Cyclooctadiene
A cyclooctadiene is a cyclic diene with the formula C8H12. Focusing only on cis derivatives, four isomers are possible: 1,2, which is an allene, 1,3-, 1,4-, and 1,5-. Commonly encountered isomers are 1,3-cyclooctadiene and 1,5-cyclooctadiene, which is used as a ligand for transition...

)2, an important reagent in organonickel chemistry.

In the presence of water scavengers, hydrated nickel(II) chloride reacts with dimethoxyethane
Dimethoxyethane
Dimethoxyethane, also known as glyme, monoglyme, dimethyl glycol, ethylene glycol dimethyl ether, dimethyl cellosolve, and DME, is a clear, colorless, aprotic, and liquid ether that is used as a solvent. Dimethoxyethane is miscible with water.Dimethoxyethane is often used as a higher boiling...

 (dme) to form the molecular complex NiCl2(dme)2. The dme ligands in this complex are labile. For example, this complex reacts with sodium cyclopentadienide
Sodium cyclopentadienide
Sodium cyclopentadienide is an organosodium compound with the formula C5H5Na. The compound is often abbreviated as NaCp or CpNa, where Cp− is the cyclopentadienide anion. Cp is also used as an abbreviation for the cyclopentadienyl ligand in coordination chemistry.-Preparation:Sodium...

 to give the sandwich compound
Sandwich compound
In organometallic chemistry, a sandwich compound is a chemical compound featuring a metal bound by haptic covalent bonds to two arene ligands. The arenes have the formula CnHn, substituted derivatives and heterocyclic derivatives...

 nickelocene
Nickelocene
Nickelocene is the organonickel compound with the formula Ni2. Also known as bisnickel or NiCp2, this bright green paramagnetic solid is of enduring academic interest, although it yet has no practical applications....

.

Applications in organic synthesis


NiCl2 and its hydrate are occasionally useful in organic synthesis
Organic synthesis
Organic synthesis is a special branch of chemical synthesis and is concerned with the construction of organic compounds via organic reactions. Organic molecules can often contain a higher level of complexity compared to purely inorganic compounds, so the synthesis of organic compounds has...

.
  • As a mild Lewis acid, e.g. for the regioselective isomerization of dienols:
  • In combination with CrCl2
    Chromium(II) chloride
    Chromium chloride is the chemical compound with the formula CrCl2. This white, crystalline solid is used for the synthesis of other chromium complexes. CrCl2 is hygroscopic. It dissolves in water to give bright blue solutions that are easily oxidized by air to give Cr-containing products...

     for the coupling of an aldehyde and a vinylic iodide to give allylic alcohols.
  • For selective reductions in the presence of LiAlH4
    Lithium aluminium hydride
    Lithium aluminium hydride, commonly abbreviated to LAH or known as LithAl, is an inorganic compound with the chemical formula LiAlH4. It was discovered by Finholt, Bond and Schlesinger in 1947. This compound is used as a reducing agent in organic synthesis, especially for the reduction of esters,...

    , e.g. for the conversion of alkenes to alkanes.
  • As a precursor to “nickel boride”, prepared in situ from NiCl2 and NaBH4
    Sodium borohydride
    Sodium borohydride, also known as sodium tetrahydridoborate, is an inorganic compound with the formula NaBH4. This white solid, usually encountered as a powder, is a versatile reducing agent that finds wide application in chemistry, both in the laboratory and on a technical scale. Large amounts are...

    . This reagent behaves like Raney Nickel, comprising an efficient system for hydrogenation of unsaturated carbonyl compounds.
  • As a precursor to finely divided Ni by reduction with Zn, for the reduction of aldehydes, alkenes, and nitro aromatic compounds. This reagent also promotes homo-coupling reactions, that is 2RX → R-R where R = aryl, vinyl.
  • As a catalyst for making dialkyl arylphosphonates from phosphites and aryl
    Aromatic hydrocarbon
    An aromatic hydrocarbon or arene is a hydrocarbon with alternating double and single bonds between carbon atoms. The term 'aromatic' was assigned before the physical mechanism determining aromaticity was discovered, and was derived from the fact that many of the compounds have a sweet scent...

     iodide, ArI:
ArI + P(OEt)3 → ArP(O)(OEt)2 + EtI

Other uses


Nickel chloride solutions are used for electroplating
Electroplating
Electroplating is a plating process in which metal ions in a solution are moved by an electric field to coat an electrode. The process uses electrical current to reduce cations of a desired material from a solution and coat a conductive object with a thin layer of the material, such as a metal...

nickel onto other metal items.

Safety


Nickel(II) chloride is irritating upon ingestion, inhalation, skin contact, and eye contact. Prolonged exposure to nickel and its compounds have been shown to produce cancer.

External links