Gold complexes dithiolates

Mansour, M.A., Lachicotte, R.J., Gysling, H.J. and Eisenberg, R. (1998) Syntheses, molecular structures, and spectroscopy of gold(III) dithiolate complexes. Inorganic Chemistry, 37, 4625. 

Terroba, R., Fernandez, E.J., Hursthouse, M.B. and Laguna, M. (1998) Dithiolate diphosphine polynuclear gold complexes. X-ray structure of [Au2( X-dppm) (C6F5)2(S2C6H4)]. Polyhedron, 17(15), 2433-2439. 

Apart from these I- I interactions, S- - S is one of the intermolecular contacts most frequently observed in gold complexes. Sulfur-rich dithiolate ligands having a planar geometry, such as C3S52 [4,5-disulfanyl-l,3-dithiole-2-thionate] or C8H4S82-[2- (4,5-ethylenedithio)-l,3-dithiole-2-ylidene -l,3-dithiole-4,5-dithionate], have been... 

Gold complexes of dithiolene ligands containing many sulfur atoms are expected to be oxidized at lower potentials. This is demonstrated by [Au(C8H4S8)2] (C8H4S8 = 2-(4,5-ethylenedithio)-l,3-dithiole-2-ylidene-l,3-dithiole-4,5-dithiolate, 5), which oxidizes very readily to the neutral complex at +0.10 V vs SCE16. The partially oxidized complex, [Au(C8H4S8)2]<5+, could also be obtained, which is of interest for molecular conductivity. 

The Au-S bond length at 2.30 A is very similar to that in the gold(III) analogue (2.299-2.312 A) and other gold(III) complexes like Au(toluene-3,4-dithiolate) (2.31 A) suggesting substantial covalent character in the bond. 

Shaw, C.F. Ill, Beery, A. and Stocco, G.C. (1986) Antitumor activity of two binudear gold(I) complexes with bridging dithiolate ligands. Inorganica Chimica Acta, 123, 213-216. 

Homoleptic gold(III) complexes with other related dithiolate ligands, as dmit (317),1855-1864 dddt,1865,1866 l,3,5-trithiepin-6,7-dithiolate,1867 dithiosquarate (318),1868,1869 6,7-dihydro-6-methy-lene-5H-l,4-dithiepine-2,3-dithiolate,1870 3,4-thiophenedithiolate (319),1637 quinoxaline-3,3-dithiolate (320),1871 2,2-diacetylethylene-1,1-dithiolate,1872 or o-carborane-1,2-dithiolate have been... 

The ligands phenylene-l,2-dithiolate, or its 4-methyl derivative, have been thoroughly studied in their gold(I) complexes and di-, tri-, and tetranuclear derivatives have been prepared of the type... 

Another important class of bidentate ligands in gold chemistry are those composed of sulfur donor ligands such as dithiocarbamates, dithiolates, dithiocarboxylates, dithiophosphinates, dithiophosphates, and so on. The complexes prepared with these ligands are generally of the type Au2(p.-SS)(PR3)2]"+ or Au2(p-SS)(p-PP)] [153-155], [Au2(p-SS)2f [156, 157] or Au3( i-SS)2(PPh3)2 [158]. All these... 

Homoleptic gold(III) derivatives with dithiolate, ligands of the type [Au(S-S)2] are well known and are usually prepared from [AuC14] with the dithiol some examples are with 1,2-benzene dithiolate, maleonitriledithiolate, dmit, and so on, [164, 336]. Similar complexes have been reported for bidentate sulfur ligands such as dithiocarbamates, dithiophosphates, and so on, [41]. Other derivatives as the trinuclear species [Au(C6F5)(S2C6H4)]3 [337] or the complex with one nido and one closo-carborane dithiolate are known [338]. Figure 1.72 collects some of these complexes. 

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