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;
UNII	3RF78267UX ;
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 labelling:
Pictograms
Signal word	Warning
Hazard statements	H315, H319, H335
Precautionary statements	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). verify (what is ?) 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]

References

^ Pierre Braunstein; Hans Lehner; Dominique Matt (1990). A Platinum-Gold Cluster: Chloro-¹κ^Cl-Bis(Triethylphosphine-¹κ^P)Bis(Triphenylphosphine)-2κP, 3κP-Triangulo- Digold-Platinum(1 ) Trifluoromethanesulfonate. Inorganic Syntheses. Vol. 27. pp. 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. Vol. 26. pp. 324–328. doi:10.1002/9780470132579.ch59. ISBN 9780470132579.
^ ^a ^b 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 (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.
^ 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.

[1] Pierre Braunstein; Hans Lehner; Dominique Matt (1990). A Platinum-Gold Cluster: Chloro-¹κ^Cl-Bis(Triethylphosphine-¹κ^P)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.

[: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 (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.

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