Fluoronickelate

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.

formula	name	Ni Ox	structure	Remarks	references
(NH₄)₂NiF₄	ammonium tetrafluoronickelate	2		Fuse NiCl₂ with NH₄F, light green color	^[1]^[2]
(NH₄)₂NiF₄·2H₂O	ammonium tetrafluoronickelate dihydrate	2		Formed from Ni(OH)₂ and NH₄F in water	^[3]
K₂NiF₄	potassium tetrafluoronickelate	2			^[1]
Rb₂NiF₄	rubidium tetrafluoronickelate	2			^[1]
Ba₂NiF₆	barium nickel fluoride	2		yellow square plates cas=18115-49-6	^[4]
Pb₂NiF₆	lead(II)nickel(II) fluoride	2		cas=27037-78-1	^[4]
Li₃NiF₆		3	Pna2 C⁹_2v a=9.60 Å b=8.37 Å c=4.09 Å Z=4 density=3.27 / 3.24	formed at 500° 70 bar F₂	^[5]^[6]
Na₃NiF₆	sodium hexafluoronickelate	3		violet cas=22707-99-9	^[4]
K₃NiF₆	potassium hexafluoronickelate	3		violet cas=14881-07-3	^[4]^[7]
KCs₂NiF₆	dicesium potassium hexafluoronickelate	3		lilac colour cas=53479-35-9	^[4]

Li₂NiF₆	lithium hexafluoronickelate	4	hexagonal a=8.321 Å c=4.598 Å V=275.7 Å³ Z=3	pink sol 0.5 g/100 g HF at 0°	^[5]^[7]
(O₂)₂NiF₆	dioxygenyl hexafluoronickelate			possibly existing, decompose 10°	^[8]^[9]
(NO₂)₂NiF₆	dinitronium hexafluoronickelate	4		ΔH=-471 kJ/mol, ΔH⁰_f=-1120	^[10]
Na₂NiF₆	sodium hexafluoronickelate	4	cubic; or tetragonal	purple red	^[11]
K₂NiF₆	potassium hexafluoronickelate	4	K₂PtCl₆ structure	red cas=17218-47-2	^[11]
CaNiF₆	calcium hexafluoronickelate	4		ΔH=-363 kJ/mol, ΔH⁰_f=-1951 kJ/mol sold as a fluorine source	^[10]
Rb₂NiF₆	rubidium hexafluoronickelate	4	K₂PtCl₆ structure	red cas=17218-48-3	^[11]
Cs₂NiF₆	Cesium hexafluoronickelate	4	K₂PtCl₆ structure	red cas=17218-49-4	^[11]
SrNiF₆	strontium hexafluoronickelate	4		red cas=66456-12-0	^[11]
BaNiF₆	barium hexafluoronickelate	4	K₂PtCl₆ structure	red cas=66456-13-1	^[11]
(NF₄)₂NiF₆	bis-tetrafluoroammonium hexafluoronickelate	4	tetragonal K₂PtCl₆ structure	red cas=63105-40-8	^[11]
(ClF₂O)NiF₆	bis [difluorooxychlorine (V)] hexafluoronickelate (IV)	4		deep purple, stable to 60 °C	^[12]^[13]

References

^ ^a ^b ^c Chaudhuri, Mihir K.; Ghosh, Soumitra K.; Hiese, Zavei (1984). "Synthesis of tetrafluoronickelate(II) and tetrafluorozincate(II) complexes from aqueous media: a novel route to fluorometalates" (PDF). Journal of the Chemical Society, Dalton Transactions (8): 1763. doi:10.1039/DT9840001763.
^ Handbook of inorganic substances 2017
^ Mellor, J. W. (May 1936). "Nickel". A COMPREHENSIVE TREATISE ON INORGANIC AND THEORETICAL CHEMISTRY VOLUME XV Ni Ru, Rh Pd, Os, Ir. p. 404. Retrieved 31 May 2016.
^ ^a ^b ^c ^d ^e Macintyre, Jane E. (1992-07-23). Dictionary of Inorganic Compounds. CRC Press. p. 3222. ISBN 9780412301209. Retrieved 25 April 2016.
^ ^a ^b Whalen, J.M.; Lucier, G.M.; Chacón, L.; Bartlett, N. (March 1998). "The room temperature conversion of nickel difluoride to hexafluoronickelate(IV) salts of alkali cations". Journal of Fluorine Chemistry. 88 (2): 107–110. doi:10.1016/S0022-1139(98)00105-5.
^ Grannec, J.; Lozano, L.; Sobre, P.; Portier, J.; Hagenmuller, P. (September 1975). "Sur un nouvel hexafluorure de nickel trivalent de formule Li3NiF6". Journal of Fluorine Chemistry (in French). 6 (3): 267–274. doi:10.1016/S0022-1139(00)83005-5.
^ ^a ^b Chacon, Lisa Carine (December 1997). "The Synthesis, Characterization and Reactivity of High Oxidation State Nickel Fluorides" (PDF). Berkeley California: University of California. Retrieved 27 April 2016.
^ Bougon, Roland A.; Christe, Karl O.; Wilson, William W. (November 1985). "Dioxygenyl salts containing doubly charged mononuclear counterions". Journal of Fluorine Chemistry. 30 (2): 237–239. doi:10.1016/S0022-1139(00)80892-1.
^ Marx, Rupert; Seppelt, Konrad (2015). "Structure investigations on oxygen fluorides". Dalton Trans. 44 (45): 19659–19662. doi:10.1039/C5DT02247A. PMID 26351980.
^ ^a ^b Vorobyov, A.F.; Solovyov, S.N.; Minasian, K.A.; Dupal, A.Ja.; Sokolov, V.B.; Spirin, S.N. (September 1991). "Thermochemistry of certain hexafluorometalates and tetrafluoroborates". Journal of Fluorine Chemistry. 54 (1–3): 333. doi:10.1016/S0022-1139(00)83842-7.
^ ^a ^b ^c ^d ^e ^f ^g Macintyre, Jane E. (1992-07-23). Dictionary of Inorganic Compounds. CRC Press. p. 3223. ISBN 9780412301209. Retrieved 25 April 2016.
^ Foulds, G.A. (February 1990). "1. Nickel". Coordination Chemistry Reviews. 98: 2. doi:10.1016/0010-8545(90)80069-6.
^ Wilson, William W.; Christe, Karl O. (September 1984). "Synthesis and characterization of bis[difluorooxychlorine(V)] hexafluoronickelate(IV), (ClF2O)2NiF6". Inorganic Chemistry. 23 (20): 3261–3262. doi:10.1021/ic00188a048.

[chaudh-1] Chaudhuri, Mihir K.; Ghosh, Soumitra K.; Hiese, Zavei (1984). "Synthesis of tetrafluoronickelate(II) and tetrafluorozincate(II) complexes from aqueous media: a novel route to fluorometalates" (PDF). Journal of the Chemical Society, Dalton Transactions (8): 1763. doi:10.1039/DT9840001763.

[2] Handbook of inorganic substances 2017

[3] Mellor, J. W. (May 1936). "Nickel". A COMPREHENSIVE TREATISE ON INORGANIC AND THEORETICAL CHEMISTRY VOLUME XV Ni Ru, Rh Pd, Os, Ir. p. 404. Retrieved 31 May 2016.

[macf6-4] Macintyre, Jane E. (1992-07-23). Dictionary of Inorganic Compounds. CRC Press. p. 3222. ISBN 9780412301209. Retrieved 25 April 2016.

[Whalen-5] Whalen, J.M.; Lucier, G.M.; Chacón, L.; Bartlett, N. (March 1998). "The room temperature conversion of nickel difluoride to hexafluoronickelate(IV) salts of alkali cations". Journal of Fluorine Chemistry. 88 (2): 107–110. doi:10.1016/S0022-1139(98)00105-5.

[6] Grannec, J.; Lozano, L.; Sobre, P.; Portier, J.; Hagenmuller, P. (September 1975). "Sur un nouvel hexafluorure de nickel trivalent de formule Li3NiF6". Journal of Fluorine Chemistry (in French). 6 (3): 267–274. doi:10.1016/S0022-1139(00)83005-5.

[Chacon-7] Chacon, Lisa Carine (December 1997). "The Synthesis, Characterization and Reactivity of High Oxidation State Nickel Fluorides" (PDF). Berkeley California: University of California. Retrieved 27 April 2016.

[8] Bougon, Roland A.; Christe, Karl O.; Wilson, William W. (November 1985). "Dioxygenyl salts containing doubly charged mononuclear counterions". Journal of Fluorine Chemistry. 30 (2): 237–239. doi:10.1016/S0022-1139(00)80892-1.

[9] Marx, Rupert; Seppelt, Konrad (2015). "Structure investigations on oxygen fluorides". Dalton Trans. 44 (45): 19659–19662. doi:10.1039/C5DT02247A. PMID 26351980.

[Voro-10] Vorobyov, A.F.; Solovyov, S.N.; Minasian, K.A.; Dupal, A.Ja.; Sokolov, V.B.; Spirin, S.N. (September 1991). "Thermochemistry of certain hexafluorometalates and tetrafluoroborates". Journal of Fluorine Chemistry. 54 (1–3): 333. doi:10.1016/S0022-1139(00)83842-7.

[macf64-11] ^ ^a ^b ^c ^d ^e ^f ^g Macintyre, Jane E. (1992-07-23). Dictionary of Inorganic Compounds. CRC Press. p. 3223. ISBN 9780412301209. Retrieved 25 April 2016.

[12] Foulds, G.A. (February 1990). "1. Nickel". Coordination Chemistry Reviews. 98: 2. doi:10.1016/0010-8545(90)80069-6.

[13] Wilson, William W.; Christe, Karl O. (September 1984). "Synthesis and characterization of bis[difluorooxychlorine(V)] hexafluoronickelate(IV), (ClF2O)2NiF6". Inorganic Chemistry. 23 (20): 3261–3262. doi:10.1021/ic00188a048.

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Fluoronickelate

References

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