Chloro(dimethyl sulfide)gold(I) explained

Chloro(dimethyl sulfide)gold(I) is a coordination complex of gold. It is a white solid. This compound is a common entry point into gold chemistry.

Structure

As for many other gold(I) complexes, the compound adopts a nearly linear (176.9°) geometry about the central gold atom. The Au-S bond distance is 2.271(2) Å, which is similar to other gold(I)-sulfur bonds.^[1]

Preparation

Chloro(dimethyl sulfide)gold(I) is commercially available. It may be prepared by dissolving gold in aqua regia (to give chloroauric acid), followed by addition of dimethyl sulfide.^[2] Alternatively, sodium tetrachloroaurate may be used as the source of gold(III).^[3] The bromo analog, Me₂SAuBr, has also been synthesized by a similar route.^[4] An approximate equation is:

HAuCl₄ + 2 SMe₂ + H₂O → Me₂SAuCl + 3 HCl + OSMe₂

A simple preparation starts from elemental gold in DMSO / conc HCl (1:2) where DMSO acts as an oxidant and the formed Me₂S as ligand. As a side product, HAuCl₄·2DMSO is formed.^[5]

Reactions

In chloro(dimethyl sulfide)gold(I), the dimethyl sulfide ligand is easily displaced by other ligands:^[6]

Me₂SAuCl + L → LAuCl + Me₂S (L = ligand)Since Me₂S is volatile, the new complex LAuCl is often easily purified.

When exposed to light, heat, or air, the compound decomposes to elemental gold.

Notes and References

1. . 44 . 12 . 1988 . 2089–2091 . 10.1107/S0108270188009151 . Chloro(dimethyl sulfide)gold(I) . P. G. Jones and J. Lautner. free .
2. 10.1039/b005251p . . 24 . 2000 . 4601–4606 . Luminescent gold(I) macrocycles with diphosphine and 4,4-bipyridyl ligands . Marie-Claude Brandys, Michael C. Jennings and Richard J. Puddephatt.
3. 10.1055/s-2007-984501 . Gold-Catalyzed Intermolecular Hydroamination of Allenes: First Example of the Use of an Aliphatic Amine in Hydroamination . 2007 . Nishina . Naoko . Yamamoto . Yoshinori . . 2007 . 11 . 1767.
4. 10.1021/ja804027j . Mitochondria-Targeted Chemotherapeutics: The Rational Design of Gold(I)N-Heterocyclic Carbene Complexes That Are Selectively Toxic to Cancer Cells and Target Protein Selenols in Preference to Thiols . 18729360 . 2008 . Hickey . James L. . Ruhayel . Rasha A. . Barnard . Peter J. . Baker . Murray V. . Berners-Price . Susan J. . Filipovska . Aleksandra . . 130 . 38 . 12570–1.
5. 10.1016/S0022-328X(97)00522-6 . Complexes of gold(I) and platinum(II) with polyaromatic phosphine ligands . 1998 . Mueller . Thomas E. . Green . Jennifer C. . Mingos . D. Michael P. . McPartlin . Jennifer C.. Whittingham . Conrad . Williams . David J. . Woodroffe . Thomas M. . . 551 . 1–2 . 313.
6. Intermolecular [2+2] Cycloaddition of Alkynes with Alkenes Catalyzed by Gold(I) . M. Elena. de Orbe. Antonio M.. Echavarren. Org. Synth.. 2016. 93. 115. 10.15227/orgsyn.093.0115. free.