Gold Chemistry

Although gold is a noble metal, it forms many and 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 tertiary phosphines. Au(I) compounds are typically linear. A good example is Au(CN)₂⁻, which is the soluble form of gold encountered in mining. Curiously, aurous complexes of water are rare. 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.

Au(III) (auric) is a common oxidation state, and is illustrated by gold(III) chloride, Au₂Cl₆. 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.

Aqua regia, a 1:3 mixture of nitric acid and hydrochloric acid, dissolves gold. 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 AuCl₄⁻ ions, or chloroauric acid, thereby enabling further oxidation.

Some free halogens react with gold. Gold also reacts in alkaline solutions of potassium cyanide. With mercury, it forms an amalgam.

Less common oxidation states

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

The −1 oxidation state occurs in compounds containing the Au⁻ anion, called aurides. Caesium auride (CsAu), for example, crystallizes in the caesium chloride motif. Other aurides include those of Rb⁺, K⁺, and tetramethylammonium (CH₃)₄N⁺.

Gold(II) compounds are usually diamagnetic with Au–Au bonds such as [Au(CH₂)₂P(C₆H₅)₂]₂Cl₂. The evaporation of a solution of Au(OH)₃ in concentrated H₂SO₄ produces red crystals of gold(II) sulfate, AuSO₄. Originally thought to be a mixed-valence compound, it has been shown to contain Au4+2 cations.^[ A noteworthy, legitimate gold(II) complex is the tetraxenonogold(II) cation, which contains xenon as a ligand, found in [AuXe₄](Sb₂F₁₁)₂.

Gold pentafluoride and its derivative anion, AuF−6, is the sole example of gold(V), the highest verified oxidation state.

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 that van der Waals bonding. The interaction is estimated to be comparable in strength to that of a hydrogen bond.

Mixed valence compounds

Well-defined cluster compounds are numerous. In such cases, gold has a fractional oxidation state. A representative example is the octahedral species {Au(P(C₆H₅)₃)}₆²⁺. Gold chalcogenides, such as gold sulfide, feature equal amounts of Au(I) and Au(III).

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