REACTIONS OF CARBONYLCHLOROGOLD(I) WITH THIOLATES AND THIOLS - CRYSTAL AND MOLECULAR-STRUCTURES OF [NAL(H2O)][(AUCL)(3)SBU(T)], [NAL][AUCL2], [NAL](4)[AUCL2](2)[AU4CL6S2] AND [NAL](2)[AU4CL6S2] (L=1,4,7,10,13-PENTAOXACYCLOPENTADECANE)

By the reaction of [AuCl(CO)] with the thiols RSH (R=Bu(t), C(6)H(3)Me (2)-2.6 or C6F5) amorphous gold(I) thiolates AU(SR) were obtained. Wit h 2,6-dimethylbenzenethiolate under CO at atmospheric pressure in CH,C I, as solvent, gold metal and RSSR were formed, while with H2S amorpho us Au2S was the product. The reaction of [AuCl(CO)] with [Na(15-crown- 5)] [SBu(t)] in 1:1 ratio yielded [Na(15-crown-5)(H2O)][(AuCl)(3)SBu(t )] 1 and [Na(15-crown-5)][AUCl(2)] 2 (15-crown-5 = 1,4,7,10,13-pentaox acyclopentadecane). The crystal structure of 1 revealed that the anion ic part contains three AuCl groups co-ordinated to the Bu(t)S(-) ligan d forming a tetrahedral arrangement around the sulfur. The [AuCl2](-) anions in 2 are co-ordinated through the chlorine atoms to two [Na(15- crown-5)](+) cations; thus, the sodium cation has a distorted pentagon al-pyramidal coordination to five oxygen atoms of the crown ether with the axial position occupied by the chlorine atoms of the AuCl2- anion . The reaction of [AuCl(CO)] with [Na(15-crown-5)][SBu(t)] in 3:1 mola r ratio afforded the mixed-valence Au-I-Au-III complexes [Na(15-crown- 5)](4)[AuCl2](2)[Au4Cl6S2] 3 and [Na(15-crown-5)](2)[Au4Cl6S2] 4. Thei r crystal structures revealed that in the [Au4Cl6S2](2-) anion two AuC l2, units are connected by the sulfur atoms of two SAuCl groups formin g a centrosymmetric planar Cl2Au(mu-S)(2)AuCl2 skeleton. The structure of 3 also contains linear [AuCl2](-) anions.