Gold(I) complexes featuring Z-type ligands introducing electron withdrawing groups (EWG), Au(DPBF)Cl (4a) and Au(DPBcl)Cl (4b) (DPB = diphosphine-boron), have been synthesized and structurally characterized. These studies suggest that increasing the electron-withdrawing properties of the boron phenyl substituent only results in minor structural changes of the gold complexes. These complexes can be converted into Au(DPBF)SbF6 and Au(DPBCl)SbF6 by treatment of 4a,b with AgSbF6. The cationic complexes show interesting catalytic properties and readily promote the cyclization of yne-diols into unprecedented dioxabicyclo [3.2.2] derivatives.