Potassium tetracyanonickelate

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Potassium tetracyanonickelate
Potassium tetracyanonickelate.svg
Potassium tetracyanonickelate.jpg
Names
Other names
Potassium tetracyanonickelate(II); dipotassium tetracyanonickelate
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
ECHA InfoCard 100.034.605 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 238-082-7
PubChem CID
UNII
  • InChI=1S/4CN.2K.Ni/c4*1-2;;;/q4*-1;2*+1;+2
    Key: LXWJYIBQIPSFSE-UHFFFAOYSA-N
  • [C-]#N.[C-]#N.[C-]#N.[C-]#N.[K+].[K+].[Ni+2]
Properties
K2Ni(CN)4
Appearanceyellow solid
Hazards
GHS labelling:
GHS-pictogram-skull.svg GHS-pictogram-pollu.svg
Danger
H300, H310, H330, H410
P260, P262, P264, P270, P271, P273, P280, P284, P301+P310, P302+P350, P304+P340, P310, P320, P321, P322, P330, P361, P363, P391, P403+P233, P405, P501
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Potassium tetracyanonickelate (IUPAC: Potassium tetracyanido nickelate(II)) is the inorganic compound with the formula K2Ni(CN)4. It is usually encountered as the monohydrate but the anhydrous salt is also known. Both are yellow, water-soluble, diamagnetic solids. The salt consists of potassium ions and the tetracyanonickelate coordination complex, which is square planar. The [Ni(CN)4]2- anions are arranged in a columnar structure with Ni---Ni distances of 4.294 Å, which is well beyond the sum of the van der Waals radius of the nickel cation. [1] . This columnar structure resembles those of the other [M(CN)4]2- anions of the heavy congeners of the group 10 metals (M = Pd, Pt).

Contents

Preparation

Ball-and-stick model of the tetracyanonickelate ion Tetracyanonickelate(II)-3D-balls.png
Ball-and-stick model of the tetracyanonickelate ion

Potassium tetracyanonickelate is prepared by treating aqueous solutions of nickel(II) salts with potassium cyanide. The synthesis is often conducted stepwise, beginning with precipitating solid nickel dicyanide coordination polymer. This route allows removal of excess potassium salts: [2]

Ni2+ + 2 KCN → Ni(CN)2 + 2 K+
Ni(CN)2 + 2 KCN → K2[Ni(CN)4]

This procedure yields the monohydrate. That solid dehydrates at 100 °C.

Reactions

The N-terminus of the cyanide ligand is basic and nucleophilic. The complex binds four equivalents of boron trifluoride:

K2[Ni(CN)4] + 4 BF3 → K2[Ni(CNBF3)4]

Cyanide is a sufficient pi-acceptor ligand to allow reduction of K2Ni(CN)4 to the Ni(0) derivative. Thus, potassium in anhydrous ammonia affords the tetraanionic, tetrahedral Ni(0) derivative [Ni(CN)4]4-. [3]

K2[Ni(CN)4] + 2 K → K4[Ni(CN)4]

An intermediate in this conversion is K4[Ni2(CN)6], which features an Ni-Ni bond. [4]

Related Research Articles

Carbon compounds 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.

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

Potassium ferrocyanide is the inorganic compound with formula K4[Fe(CN)6]·3H2O. It is the potassium salt of the coordination complex [Fe(CN)6]4−. This salt forms lemon-yellow monoclinic crystals.

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

Sodium cyanide is a poisonous compound with the formula NaCN. It is a white, water-soluble solid. Cyanide has a high affinity for metals, which leads to the high toxicity of this salt. Its main application, in gold mining, also exploits its high reactivity toward metals. It is a moderately strong base.

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

Nickel(II) chloride (or just nickel chloride) is the chemical compound NiCl2. The anhydrous salt is yellow, but the more familiar hydrate NiCl2·6H2O is green. Nickel(II) chloride, in various forms, is the most important source of nickel for chemical synthesis. The nickel chlorides are deliquescent, absorbing moisture from the air to form a solution. Nickel salts have been shown to be carcinogenic to the lungs and nasal passages in cases of long-term inhalation exposure.

<span class="mw-page-title-main">Nickel(II) fluoride</span> Chemical compound

Nickel(II) fluoride is the chemical compound with the formula NiF2. It is an ionic compound of nickel and fluorine and forms yellowish to green tetragonal crystals. Unlike many fluorides, NiF2 is stable in air.

<span class="mw-page-title-main">Metal dithiolene complex</span>

Dithiolene metal complexes are complexes containing 1,2-dithiolene ligands. 1,2-Dithiolene ligands, a particular case of 1,2-dichalcogenolene species along with 1,2-diselenolene derivatives, are unsaturated bidentate ligand wherein the two donor atoms are sulfur. 1,2-Dithiolene metal complexes are often referred to as "metal dithiolenes", "metallodithiolenes" or "dithiolene complexes". Most molybdenum- and tungsten-containing proteins have dithiolene-like moieties at their active sites, which feature the so-called molybdopterin cofactor bound to the Mo or W.

<span class="mw-page-title-main">Tetrafluoroborate</span> Anion

Tetrafluoroborate is the anion BF
4
. This tetrahedral species is isoelectronic with tetrafluoroberyllate (BeF2−
4
), tetrafluoromethane (CF4), and tetrafluoroammonium (NF+
4
) and is valence isoelectronic with many stable and important species including the perchlorate anion, ClO
4
, which is used in similar ways in the laboratory. It arises by the reaction of fluoride salts with the Lewis acid BF3, treatment of tetrafluoroboric acid with base, or by treatment of boric acid with hydrofluoric acid.

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

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.

<span class="mw-page-title-main">Metal nitrosyl complex</span> Complex of a transition metal bonded to nitric oxide: Me–NO

Metal nitrosyl complexes are complexes that contain nitric oxide, NO, bonded to a transition metal. Many kinds of nitrosyl complexes are known, which vary both in structure and coligand.

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

Tetraphenylphosphonium chloride is the chemical compound with the formula (C6H5)4PCl, abbreviated Ph4PCl or PPh4Cl. Tetraphenylphosphonium and especially tetraphenylarsonium salts were formerly of interest in gravimetric analysis of perchlorate and related oxyanions. This colourless salt is used to generate lipophilic salts from inorganic and organometallic anions. Thus, Ph4P+ is useful as a phase-transfer catalyst, again because it allows inorganic anions to dissolve in organic solvents.

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

Potassium hexacyanochromate(III) is an inorganic compound with the formula K3[Cr(CN)6]. It consists of three potassium cations and [Cr(CN)6]3− anion. It is a yellow, air-stable, paramagnetic solid. It is isomorphous with potassium ferricyanide.

Cobalt(II) cyanide is the inorganic compound with the formula Co(CN)2. It is coordination polymer that has attracted intermittent attention over many years in the area of inorganic synthesis and homogeneous catalysis.

<span class="mw-page-title-main">Nickel(II) bis(acetylacetonate)</span> Coordination complex

Nickel(II) bis(acetylacetonate) is a coordination complex with the formula [Ni(acac)2]3, where acac is the anion C5H7O2 derived from deprotonation of acetylacetone. It is a dark green paramagnetic solid that is soluble in organic solvents such as toluene. It reacts with water to give the blue-green diaquo complex Ni(acac)2(H2O)2.

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

In organometallic chemistry, a dicarbollide is an anion of the formula [C2B9H11]2-. Various isomers exist, but most common is 1,2-dicarbollide derived from ortho-carborane. These dianions function as ligands, related to the cyclopentadienyl anion. Substituted dicarbollides are also known such as [C2B9H10(pyridine)] (pyridine bonded to B) and [C2R2B9H9]2- (R groups bonded to carbon).

Cyanometallates or cyanometalates are a class of coordination compounds, most often consisting only of cyanide ligands. Most are anions. Cyanide is a highly basic and small ligand, hence it readily saturates the coordination sphere of metal ions. The resulting cyanometallate anions are often used as building blocks for more complex structures called coordination polymers, the best known example of which is Prussian blue, a common dyestuff.

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

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 contain the [Ni(CN)4]2− anion. This can exist in solution or in solid salts. The ion has cyanide groups arranged in a square around the central nickel ion. The symmetry of the ion is D4h. The distance from the nickel atom to the carbon is 1.87 Å, and the carbon-nitrogen distance is 1.16 Å. In their crystals, the tetracyanonickelate(II) anions are often arranged in a columnar structure (e.g. in K2[Ni(CN)4]). Tetracyanonickelate(II) can be oxidised electrochemically in solution to yield tetracyanonickelate(III) [Ni(CN)4]. [Ni(CN)4] is unstable and Ni(III) oxidises the cyanide to cyanate OCN. Tetracyanonickelate(III) can add two more cyanide groups to form hexacyanonickelate(III).

Nickel compounds 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.

The fluoronickelates are a class of chemical compounds containing an anion with nickel at its core, surrounded by fluoride ions which act as ligands. This makes it a fluoroanion. The nickel atom can be in a range of oxidation states from +2, +3 to +4. The hexafluoronickelate(IV)2− ion NiF62− contains nickel in the maximal +4 state, and is in octahedral coordination by the fluoride atoms. It forms a commercially available salt Potassium hexafluoronickelate(IV) K2NiF6. Solid double salts can also contain tetrafluoronickelate NiF4 eg K2NiF4.

Nickel dicyanide is the inorganic compound with a chemical formula Ni(CN)2. It is a gray-green solid that is insoluble in most solvents.

<span class="mw-page-title-main">Potassium octacyanomolybdate(IV)</span> Chemical compound

Potassium octacyanomolybdate(IV) is the inorganic salt with the formula K4[Mo(CN)8]. A yellow light-sensitive solid, it is the potassium salt of the cyanometalate with the coordination number eight. The complex anion consists of a Mo(IV) center bound to eight cyanide ligands resulting in an overall charge of −4, which is balanced with four potassium cations. The salt is often prepared as its dihydrate K4[Mo(CN)8].(H2O)2.

References

  1. Vannerberg, Nils Gosta (1964). "The Crystal Structure of K2Ni(CN)4" (PDF). Acta Chemica Scandinavica. 18 (10): 2385–2391. doi: 10.3891/acta.chem.scand.18-2385 . Retrieved 29 April 2016. ICSD number 24099
  2. Fernelius, W. C.; Burbage, Joseph J. (1946). "Potassium Tetracyanonickelate(II)". Inorganic Syntheses. Inorganic Syntheses. Vol. 2. pp. 227–228. doi:10.1002/9780470132333.ch73. ISBN   9780470132333.
  3. Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. p. 426. ISBN   978-0-08-037941-8.
  4. Jarchow, O.; Schulz, H.; Nast, R. (1970). "Structure of the Anion in Solid K4[Ni2(CN)6]". Angewandte Chemie International Edition in English. 9: 71. doi:10.1002/anie.197000711.