Chloro(triphenylphosphine)gold(I)

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Chloro(triphenylphosphine)gold(I)
PPh3AuCl.png
Chloro(triphenylphosphine)gold(I)-3D-spacefill.png
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.034.636 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 238-117-6
PubChem CID
UNII
  • InChI=1S/C18H15P.Au.ClH/c1-4-10-16(11-5-1)19(17-12-6-2-7-13-17)18-14-8-3-9-15-18;;/h1-15H;;1H/q;+1;/p-1 X mark.svgN[ pubchem ]
    Key: IFPWCRBNZXUWGC-UHFFFAOYSA-M X mark.svgN
  • separate form:C1=CC=C(C=C1)P(C2=CC=CC=C2)C3=CC=CC=C3.Cl[Au]
  • coordination form:Cl[Au-][P+](c0ccccc0)(c0ccccc0)c0ccccc0
Properties
C18H15AuClP
Molar mass 494.71 g·mol−1
AppearanceColorless solid
Density 1.97 g/cm3
Melting point 236–237 °C (457–459 °F; 509–510 K)
Hazards
GHS labelling:
GHS-pictogram-exclam.svg
Warning
H315, H319, H335
P261, P264, P271, P280, P302+P352, P304+P340, P305+P351+P338, P312, P321, P332+P313, P337+P313, P362, P403+P233, P405, P501
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Chloro(triphenylphosphine)gold(I) or triphenylphosphinegold(I) chloride is a coordination complex with the formula (Ph 3P)AuCl. This colorless solid is a common reagent for research on gold compounds.

Contents

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]

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

  1. Pierre Braunstein; Hans Lehner; Dominique Matt (1990). A Platinum-Gold Cluster: Chloro-1κCl-Bis(Triethylphosphine-1κP)Bis(Triphenylphosphine)-2κP, 3κP-Triangulo- Digold-Platinum(1 +) Trifluoromethanesulfonate. Inorganic Syntheses. Vol. 27. pp. 218–221. doi:10.1002/9780470132586.ch42.
  2. M. I. Bruce; B. K. Nicholson; O. Bin Shawkataly (1989). "Synthesis of Gold-Containing Mixed-Metal Cluster Complexes". Inorganic Syntheses. Vol. 26. pp. 324–328. doi:10.1002/9780470132579.ch59. ISBN   9780470132579.
  3. 1 2 Gorin, David J.; Sherry, Benjamin D.; Toste, F. Dean (2008), "Triphenylphosphinegold(I) chloride", Encyclopedia of Reagents for Organic Synthesis, American Cancer Society, doi:10.1002/047084289x.rn00803, ISBN   9780470842898
  4. Baenziger, N. C.; Bennett, W. E.; Soborofe, D. M. (1976). "Chloro(triphenylphosphine)gold(I)". Acta Crystallographica Section B. 32 (3): 962. doi:10.1107/S0567740876004330.
  5. Borissova, Alexandra O.; Korlyukov, Alexander A.; Antipin, Mikhail Yu.; Lyssenko, Konstantin A. (2008). "Estimation of Dissociation Energy in Donor−Acceptor Complex AuCl·PPh3via Topological Analysis of the Experimental Electron Density Distribution Function". The Journal of Physical Chemistry A. 112 (46): 11519–22. doi:10.1021/jp807258d. PMID   18959385.
  6. Mézailles, Nicolas; Ricard, Louis; Gagosz, Fabien (2005-09-01). "Phosphine Gold(I) Bis-(trifluoromethanesulfonyl)imidate Complexes as New Highly Efficient and Air-Stable Catalysts for the Cycloisomerization of Enynes". Organic Letters. 7 (19): 4133–4136. doi:10.1021/ol0515917. ISSN   1523-7060. PMID   16146370.
  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. doi : 10.1002/9780470132609.ch63
  8. Rice, Gary W.; Tobias, R. Stuart (1976). "Isolation of thermally stable compounds containing the dimethylaurate(I) and tetramethylaurate(III) anions" . Inorganic Chemistry. 15 (2): 489–490. doi:10.1021/ic50156a058. ISSN   0020-1669.
  9. Zhu, Dunming; Lindeman, Sergey V.; Kochi, Jay K. (1999). "X-ray Crystal Structures and the Facile Oxidative (Au−C) Cleavage of the Dimethylaurate(I) and Tetramethylaurate(III) Homologues" . Organometallics. 18 (11): 2241–2248. doi:10.1021/om990043s. ISSN   0276-7333.