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Potassium tetracyanonickelate

From Wikipedia, the free encyclopedia
Potassium tetracyanonickelate
Names
Other names
Potassium tetracyanonickelate(II); dipotassium tetracyanonickelate
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
ECHA InfoCard100.034.605Edit this at Wikidata
EC Number
  • 238-082-7
UNII
  • InChI=1S/4CN.2K.Ni/c4*1-2;;;/q4*-1;2*+1;+2
    Key: LXWJYIBQIPSFSE-UHFFFAOYSA-N
  • [K+].[K+].[N-]#C[Ni+2](C#[N-])(C#[N-])C#[N-]
Properties
K2Ni(CN)4
Appearanceyellow solid
Hazards
GHS labelling:
GHS06: ToxicGHS09: Environmental hazard
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 theirstandard state (at 25 °C [77 °F], 100 kPa).
Chemical compound

Potassium tetracyanonickelate (IUPAC: Potassium tetracyanido nickelate(II)) is theinorganic 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 thetetracyanonickelate 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 thevan 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).

Preparation

[edit]
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 solidnickel dicyanidecoordination 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

[edit]

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

K2[Ni(CN)4] + 4 BF3 → K2[Ni(CNBF3)4]

Cyanide is a sufficientpi-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]

References

[edit]
  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. Retrieved29 April 2016. ICSD number 24099
  2. ^Fernelius, W. C.; Burbage, Joseph J. (1946). "Potassium Tetracyanonickelate(II)".Inorganic Syntheses. Vol. 2. pp. 227–228.doi:10.1002/9780470132333.ch73.ISBN 9780470132333.{{cite book}}:ISBN / Date incompatibility (help)
  3. ^Greenwood, Norman N.; Earnshaw, Alan (1997).Chemistry of the Elements (2nd ed.).Butterworth-Heinemann. p. 426.doi:10.1016/C2009-0-30414-6.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.
Nickel(0)
Nickel(II)
Nickel(III)
Nickel(IV)
Salts and covalent derivatives of thecyanide ion
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