The preparation and coordination chemistry of substituted benzenethiols. Triphenylphosphine gold(I) complexes of sterically demanding and nondemanding arenethiols. The absence of gold(I)-gold(I) interactions

Novel substituted benzenethiols can be easily prepared via aryl thiocyanate s or aryl bromides. Reaction of [(Ph3P)AuCl] with the sterically-nondemandi ng benzenethiols HSC6H4NMe2-p and HSC6H4NMe3+-p and with the sterically-dem anding benzenethiols HSCMe2H2NMe2-p, HSC6Me4H-p and in the presence of trie thylamine yields the monomeric gold(I) complexes [(Ph3P)Au(SAr)], which are analogous to the gold-based antiarthritic drug Auranofin. Reaction with th e sterically demanding dithiol HSC6Me4SH-p in the presence of NEt3 yields t he dimeric complex [{(Ph3P)Au}(2)(mu-SC6Me4S-p)]. Spectrochemical and elect rochemical data are reported. The crystal structures of [(Ph3P)Au(SC6HNMe2- p)] and [(Ph3P)Au(SC6H4NMe3-p)]PF6 have been solved: both complexes are mon omeric in the solid state, lacking the short gold-gold interaction which is commonly found in gold(I) complexes of soft ligands, e.g., [(Ph3P)Au(SPh)] (2). (C) 1998 Elsevier Science Ltd. All rights reserved.