Starting with 1,2-dibromobenzene and 1,2,3,4-tetrafluorobenzene, dimethyl(2-(trimethylstannyl)phenyl)phosphane, Me₂P(o-C₆H₄)SnMe₃, and dimethyl-[2,3,4,5-tetrafluoro-6-(trimethylstannyl)phenyl]phosphane, Me₂P(o-C₆F₄)SnMe₃, were synthesized and used in tin-gold exchange reactions to prepare two gold(I) dimers, bis[(2-dimethylphosphino)phenyl]di-gold(I), [Au₂(μ-2-C₆H₄PMe₂)₂], and bis[(2-dimethylphosphino)-3,4,5,6-tetrafluorophenyl]di-gold(I), [Au₂(μ-2-C₆F₄PMe₂)₂], respectively. Both tin precursor molecules, as well as the gold(I) complexes, were characterized by multinuclear NMR spectroscopy, CHN analysis and X-ray diffraction experiments. Both gold(I) dimers were further investigated by the means of computational as well as photophysical methods.