Reactions of carbonylchlorogold(I) with thiolates and thiols. Crystal and molecular structures of [NaL(H2O)][(AuCl)3SBut], [NaL][AuCl2], [NaL]4[AuCl2]2[Au4Cl6S2] and [NaL]2[Au4Cl6S2](L = 1,4,7,10,13-pentaoxacyclopentadecane)

Abstract

By the reaction of [AuCl(CO)] with the thios RSH (R = Bu^t, C₆H₃Me₂-2,6 or C₆F₅) amorphous gold(I) thiolates Au(SR) were obtained. With 2,6-dimethylbenzenethiolate under CO at atomospheric pressure in CH₂Cl₂ as solvent, gold metal and RSSR were formed, while with H₂S amorphous 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)₃SBu^t]1 and [Na(15-crown-5)][AuCl₂]2(15-crown-5 = 1,4,7,10,13-pentaoxacyclopentadecane). The crystal structure of 1 revealed that the anionic part contains three AuCl groups co-ordinated to the Bu^tS^– ligand 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 pentagonal-pyramidal co-ordination 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 molar 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. There crystal structures revelaed that in the [Au₄Cl₆S₂]^2–-anion two AuCl₂ units are connected by the sulfur atoms of two SAuCl groups forming a centrosymmetric planar Cl₂Au(µ-S)₂AuCl₂skeleton. The structure of 3 also contains linear [AuCl₂]^– anions.