Английская Википедия:Chloro(triphenylphosphine)gold(I)

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Шаблон:Chembox Chloro(triphenylphosphine)gold(I) or triphenylphosphinegold(I) chloride is a coordination complex with the formula (Ph3P)AuCl. This colorless solid is a common reagent for research on gold compounds.

Preparation and structure

The complex is prepared by reducing chloroauric acid with triphenylphosphine in 95% ethanol:[1][2]

HAuCl4 + H2O + 2 PPh3 → (Ph3P)AuCl + Ph3PO + 3 HCl

Ph3PAuCl can also be prepared by treating a thioether complex of gold like (dimethyl sulfide)gold(I) chloride, [(Me2S)AuCl], with triphenylphosphine.[3]

The complex adopts a linear coordination geometry, which is typical of most gold(I) compounds.[4] It crystallizes in the orthorhombic space group P212121 with a = 12.300(4) Å, b = 13.084(4) Å, c = 10.170(3) Å with Z = 4 formula units per unit cell. [5]

Reactivity

Triphenylphosphinegold(I) chloride is a popular stable precursor for a cationic gold(I) catalyst used in organic synthesis.[3] Typically, it is treated with silver(I) salts of weakly coordinating anions (e.g., X– = SbF6–, BF4–, TfO–, or Tf2N–) to generate a weakly bound Ph3PAu–X complex, in equilibrium with the catalytically-active species [Ph3PAu]+X– in solution. Among these, only the bistriflimide complex Ph3PAuNTf2 can be isolated as the pure compound.[6] The nitrate complex Ph3PAuONO2 and the oxonium species [(Ph3PAu)3O]+[BF4]– are also prepared from the chloride.[7]

As shown in the scheme below, the methyl complex Ph3PAuMe is prepared from triphenylphosphinegold(I) chloride by transmetalation with a Grignard reagent. Further treatment of Ph3PAuMe with methyllithium displaces the phosphine ligand and generates lithium di- and tetramethylaurate, Li+[AuMe2]– and Li+[AuMe4]–, respectively.[8] [9]

Файл:Reaction scheme of gold(I) and gold(III) organometallic compounds.png
Reaction scheme of Au(I) and Au(III) organometallic compounds, with (Ph3P)AuCl as the precursor.

References

Шаблон:Reflist Шаблон:Gold compounds

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  1. ↑ Шаблон:Cite book
  2. ↑ Шаблон:Cite book
  3. ↑ 3,0 3,1 Шаблон:Citation
  4. ↑ Шаблон:Cite journal
  5. ↑ Шаблон:Cite journal
  6. ↑ Шаблон:Cite journal
  7. ↑ A. M. Mueting, B. D. Alexander, P. D. Boyle, A. L. Casalnuovo, L. N. Ito, B. J. Johnson, L. H. Pignolet "Mixed-Metal-Gold Phosphine Cluster Compounds" Inorganic Syntheses, 1992, Volume 29, Pages 279–298, 2007. Шаблон:Doi
  8. ↑ Шаблон:Cite journal
  9. ↑ Шаблон:Cite journal
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