Novel tosyl- and mesitylsulfonyl-substituted triazaphospholes were synthesized and structurally characterized. In an attempt to prepare the corresponding Au(I)-complexes with stoichiometric amounts of AuCl·S(CH3)2, cyclo-1,3-diphospha(III)-2,4-diazane-AuCl-complexes were obtained instead. Our here presented results offer a new strategy for preparing such coordination compounds selectively in a one-pot approach.