Chemistry:Gold compounds

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Gold(III) chloride solution in water

Gold compounds are compounds by the element gold (Au). Although gold is the most noble of the noble metals,[1][2] it still forms many diverse compounds. The oxidation state of gold in its compounds ranges from −1 to +5, but Au(I) and Au(III) dominate its chemistry. Au(I), referred to as the aurous ion, is the most common oxidation state with soft ligands such as thioethers, thiolates, and organophosphines. Au(I) compounds are typically linear. A good example is Au(CN)−
2, which is the soluble form of gold encountered in mining. The binary gold halides, such as AuCl, form zigzag polymeric chains, again featuring linear coordination at Au. Most drugs based on gold are Au(I) derivatives.[3]

Au(III) (referred to as the auric) is a common oxidation state, and is illustrated by gold(III) chloride, Au
2Cl
6. The gold atom centers in Au(III) complexes, like other d8 compounds, are typically square planar, with chemical bonds that have both covalent and ionic character. Gold(I,III) chloride is also known, an example of a mixed-valence complex.

Gold does not react with oxygen at any temperature[4] and, up to 100 °C, is resistant to attack from ozone.[5]

[math]\displaystyle{ \mathrm{Au}+\mathrm{O}_2 \neq }[/math]
[math]\displaystyle{ \mathrm{Au}+\mathrm{O}_3 \overset{\underset{t\lt 100^\circ\text{C}}{}}{\neq} }[/math]

Some free halogens react with gold.[6] Gold is strongly attacked by fluorine at dull-red heat[7] to form gold(III) fluoride AuF
3. Powdered gold reacts with chlorine at 180 °C to form gold(III) chloride AuCl
3.[8] Gold reacts with bromine at 140 °C to form gold(III) bromide AuBr
3, but reacts only very slowly with iodine to form gold(I) iodide AuI.

[math]\ce{ 2 Au + 3 F2 ->[t] 2 AuF3 }[/math]
[math]\ce{ 2 Au + 3 Cl2 ->[t] 2 AuCl3 }[/math]
[math]\ce{ 2 Au + 2 Br2 ->[t] AuBr3 + AuBr }[/math]
[math]\ce{ 2 Au + I2 ->[t] 2 AuI }[/math]

Gold does not react with sulfur directly,[9] but gold(III) sulfide can be made by passing hydrogen sulfide through a dilute solution of gold(III) chloride or chloroauric acid.

Gold readily dissolves in mercury at room temperature to form an amalgam, and forms alloys with many other metals at higher temperatures. These alloys can be produced to modify the hardness and other metallurgical properties, to control melting point or to create exotic colors.[10]

Gold is unaffected by most acids. It does not react with hydrofluoric, hydrochloric, hydrobromic, hydriodic, sulfuric, or nitric acid. It does react with selenic acid, and is dissolved by aqua regia, a 1:3 mixture of nitric acid and hydrochloric acid. Nitric acid oxidizes the metal to +3 ions, but only in minute amounts, typically undetectable in the pure acid because of the chemical equilibrium of the reaction. However, the ions are removed from the equilibrium by hydrochloric acid, forming AuCl−
4 ions, or chloroauric acid, thereby enabling further oxidation.

[math]\ce{ 2Au {}+ 6 H2SeO4 ->[200^\circ C] Au2(SeO4)3 {}+ 3 H2SeO3 {}+ 3H2O }[/math]
[math]\ce{ Au {}+ 4 HCl {}+ HNO3 -> H[AuCl4] {}+ NO\uparrow + 2H2O }[/math]

Gold is similarly unaffected by most bases. It does not react with aqueous, solid, or molten sodium or potassium hydroxide. It does however, react with sodium or potassium cyanide under alkaline conditions when oxygen is present to form soluble complexes.[9]

Common oxidation states of gold include +1 (gold(I) or aurous compounds) and +3 (gold(III) or auric compounds). Gold ions in solution are readily reduced and precipitated as metal by adding any other metal as the reducing agent. The added metal is oxidized and dissolves, allowing the gold to be displaced from solution and be recovered as a solid precipitate.

Rare oxidation states

Less common oxidation states of gold include −1, +2, and +5.

The −1 oxidation state occurs in aurides, compounds containing the Au−
 anion. Caesium auride (CsAu), for example, crystallizes in the caesium chloride motif;[11] rubidium, potassium, and tetramethylammonium aurides are also known.[12] Gold has the highest electron affinity of any metal, at 222.8 kJ/mol, making Au−
 a stable species,[13] analogous to the halides.

Gold also has a –1 oxidation state in covalent complexes with the group 4 transition metals, such as in titanium tetraauride and the analogous zirconium and hafnium compounds. These chemicals are expected to form gold-bridged dimers in a manner similar to titanium(IV) hydride.[14]

Gold(II) compounds are usually diamagnetic with Au–Au bonds such as [Au(CH
2)
2P(C
6H
5)
2]
2Cl
2. The evaporation of a solution of Au(OH)
3 in concentrated H
2SO
4 produces red crystals of gold(II) sulfate, Au
2(SO
4)
2. Originally thought to be a mixed-valence compound, it has been shown to contain Au4+
2 cations, analogous to the better-known mercury(I) ion, Hg2+
2.[15][16] A gold(II) complex, the tetraxenonogold(II) cation, which contains xenon as a ligand, occurs in [AuXe
4](Sb
2F
11)
2.[17]

Gold pentafluoride, along with its derivative anion, AuF−
6, and its difluorine complex, gold heptafluoride, is the sole example of gold(V), the highest verified oxidation state.[18]

Some gold compounds exhibit aurophilic bonding, which describes the tendency of gold ions to interact at distances that are too long to be a conventional Au–Au bond but shorter than van der Waals bonding. The interaction is estimated to be comparable in strength to that of a hydrogen bond.

Well-defined cluster compounds are numerous.[12] In some cases, gold has a fractional oxidation state. A representative example is the octahedral species {Au(P(C
6H
5)
3)}2+
6.

See also

References

  1. ↑ Hammer, B.; Norskov, J. K. (1995). "Why gold is the noblest of all the metals". Nature 376 (6537): 238–240. doi:10.1038/376238a0. Bibcode: 1995Natur.376..238H. 
  2. ↑ Johnson, P. B.; Christy, R. W. (1972). "Optical Constants of the Noble Metals". Physical Review B 6 (12): 4370–4379. doi:10.1103/PhysRevB.6.4370. Bibcode: 1972PhRvB...6.4370J. 
  3. ↑ Shaw III, C. F. (1999). "Gold-Based Medicinal Agents". Chemical Reviews 99 (9): 2589–2600. doi:10.1021/cr980431o. PMID 11749494. 
  4. ↑ "Chemistry of Oxygen". 2 October 2013. http://chemwiki.ucdavis.edu/Core/Inorganic_Chemistry/Descriptive_Chemistry/Elements_Organized_by_Block/2_p-Block_Elements/Group_16%253A_The_Oxygen_Family/Chemistry_of_Oxygen. 
  5. ↑ Handbook of Corrosion Data. Materials Park, Ohio: ASM International. 1995. p. 587. ISBN 978-0-87170-518-1. 
  6. ↑ Wiberg, Egon; Wiberg, Nils; Holleman, Arnold Frederick (2001). Inorganic Chemistry (101st ed.). Academic Press. p. 1286. ISBN 978-0-12-352651-9. 
  7. ↑ Wiberg, Egon; Wiberg, Nils (2001). Inorganic Chemistry. Academic Press. p. 404. ISBN 978-0-12-352651-9. https://books.google.com/books?id=Mtth5g59dEIC. 
  8. ↑ Wiberg, Wiberg & Holleman 2001, pp. 1286–1287
  9. ↑ 9.0 9.1 Emery, J. F.; Ledditcotte, G. W. (May 1961). "Nuclear Science Series (NAS-NS 3036) The Radio Chemistry of Gold". Oak Ridge, TN: National Academy of Sciences — National Research Council — Subcommittee on Radio Chemistry. http://library.lanl.gov/cgi-bin/getfile?rc000062.pdf. 
  10. ↑ Jewellery Alloys. World Gold Council
  11. ↑ Jansen, Martin (2005). "Effects of relativistic motion of electrons on the chemistry of gold and platinum". Solid State Sciences 7 (12): 1464–1474. doi:10.1016/j.solidstatesciences.2005.06.015. Bibcode: 2005SSSci...7.1464J. 
  12. ↑ 12.0 12.1 Holleman, A. F.; Wiberg, E. (2001). Inorganic Chemistry. San Diego: Academic Press. ISBN 978-0-12-352651-9. 
  13. ↑ Jansen, Martin (2008). "The chemistry of gold as an anion". Chemical Society Reviews 37 (9): 1826–1835. doi:10.1039/b708844m. PMID 18762832. 
  14. ↑ Jung, Jaehoon; Kim, Hyemi; Kim, Jong Chan; Park, Min Hee; Han, Young-Kyu (2011). "Gold Behaves as Hydrogen in the Intermolecular Self-Interaction of Metal Aurides MAu4 (M=Ti, Zr, and Hf)". Chemistry: An Asian Journal 6 (3): 868–872. doi:10.1002/asia.201000742. PMID 21225974. 
  15. ↑ Wickleder, Mathias S. (2001). "AuSO4: A True Gold(II) Sulfate with an Au24+ Ion". Journal of Inorganic and General Chemistry 627 (9): 2112–2114. doi:10.1002/1521-3749(200109)627:9<2112::AID-ZAAC2112>3.0.CO;2-2. 
  16. ↑ Wickleder, Mathias S. (2007). Devillanova, Francesco A.. ed. Handbook of chalcogen chemistry: new perspectives in sulfur, selenium and tellurium. Royal Society of Chemistry. pp. 359–361. ISBN 978-0-85404-366-8. https://books.google.com/books?id=IvGnUAaSqOsC&pg=PA359. 
  17. ↑ Seidel, S.; Seppelt, K. (2000). "Xenon as a Complex Ligand: The Tetra Xenono Gold(II) Cation in AuXe42+(Sb2F11−)2". Science 290 (5489): 117–118. doi:10.1126/science.290.5489.117. PMID 11021792. Bibcode: 2000Sci...290..117S. 
  18. ↑ Riedel, S.; Kaupp, M. (2006). "Revising the Highest Oxidation States of the 5d Elements: The Case of Iridium(+VII)". Angewandte Chemie International Edition 45 (22): 3708–3711. doi:10.1002/anie.200600274. PMID 16639770. 



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