The mechanism of action of auranofin, an antiarthritic gold(I) drug,is unknown, but several studies suggest that oxidation may beimportant for its biochemical effect. Bulk electrolysis studies onauranofin [(Et
3P)Au(TATG); TATG = 2,3,4,6-tetraacetyl-1-thio-
D-glucopyranosato] at +1.2 and +1.6 V versus Ag/AgCl in 0.1 MBu
4NBF
4/CH
2Cl
2 results in
n values of 0.5 and >2 electrons,respectively. Oxidation of auranofin with the mild oxidant, Cp
2Fe
+,results in formation of disulfide and a digold(I) cation with a bridgingthiolate ligand, [(Et
3PAu)
2(
![](/images/entities/mgr.gif)
-TATG)]
+ (
1). The X-ray structure ofthe PMe
3 analogue, [(Me
3PAu)
2(
![](/images/entities/mgr.gif)
-TATG)](NO
3) (
2), is reported.Compound
2 forms a tetranuclear cluster containing an almostperfect square of four gold atoms with Au···Au distances averaging3.14 Å. The complex crystallizes in the tetragonal space group
P4
22
12 with cell constants
a = 26.1758(6) Å,
b = 26.1758(6) Å,
c = 9.7781(3) Å,
![](/images/gifchars/alpha.gif)
=
![](/images/gifchars/beta2.gif)
=
![](/images/gifchars/gamma.gif)
= 90
![](/images/entities/deg.gif)
,
V = 6699.7(3) Å
3,
Z = 4,R1 = 0.0644, and wR2 = 0.1152. A mechanism for oxidation ofauranofin and possible biological implications are discussed.