Chloro(triphenylphosphine)gold(I)

Chloro(triphenylphosphine)gold(I)
Identifiers
CAS Number	14243-64-2 ;
3D model (JSmol)	separate form: Interactive image; coordination form: Interactive image;
ChemSpider	62872670 ;
ECHA InfoCard	100.034.636
EC Number	238-117-6;
PubChem CID	10874691;
CompTox Dashboard (EPA)	DTXSID40931445 ;
	InChI 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 [pubchem] Key: IFPWCRBNZXUWGC-UHFFFAOYSA-M ;
	SMILES 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
Chemical formula	C18H15AuClP
Molar mass	494.71 g·mol−1
Appearance	Colorless solid
Density	1.97 g/cm3
Melting point	236–237 °C (457–459 °F; 509–510 K)
Hazards
GHS pictograms
GHS Signal word	Warning
GHS hazard statements	H315, H319, H335
GHS precautionary statements	P261, P264, P271, P280, P302+352, P304+340, P305+351+338, P312, P321, P332+313, P337+313, P362, P403+233, 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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	Infobox references

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]

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

References

Pierre Braunstein, Hans Lehner, Dominique Matt "A Platinum-Gold Cluster: Chloro-¹κ^Cl-Bis(Triethylphosphine-¹κ^P)Bis(Triphenylphosphine)-2κP, 3κP-Triangulo- Digold-Platinum(1 +) Trifluoromethanesulfonate" Inorganic Syntheses, 1990, Volume 27, Pages 218–221. doi: 10.1002/9780470132586.ch42
M. I. Bruce, B. K. Nicholson, O. Bin Shawkataly (1989). "Synthesis of Gold-Containing Mixed-Metal Cluster Complexes". Inorganic Syntheses. Inorganic Syntheses. 26. pp. 324–328. doi:10.1002/9780470132579.ch59. ISBN 9780470132579.CS1 maint: uses authors parameter (link)
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
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.
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.
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.
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
Rice, Gary W.; Tobias, R. Stuart. "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.
Zhu, Dunming; Lindeman, Sergey V.; Kochi, Jay K. "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.

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[1] Pierre Braunstein, Hans Lehner, Dominique Matt "A Platinum-Gold Cluster: Chloro-¹κ^Cl-Bis(Triethylphosphine-¹κ^P)Bis(Triphenylphosphine)-2κP, 3κP-Triangulo- Digold-Platinum(1 +) Trifluoromethanesulfonate" Inorganic Syntheses, 1990, Volume 27, Pages 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. Inorganic Syntheses. 26. pp. 324–328. doi:10.1002/9780470132579.ch59. ISBN 9780470132579.CS1 maint: uses authors parameter (link)

[:0-3] 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. "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. "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.