Vibrational interactions in dimethylgold(III) halides and carboxylates

The far-infrared and Raman spectra of binuclear molecules Me₂AuX]₂ (X = Cl, Br, I) and Me₂Au(OOCR)]₂ (R = Me, CF₃, Bu^t, Ph) in the 600–70 cm⁻¹ region are reported. The experimentally measured vibrational frequencies of Me₂AuX]₂ are in a good agreement with density functional theory predictions. The Au…Au vibrational interactions predicted to be in the 270–60 cm⁻¹ region of Me₂AuX]₂ far-IR and Raman spectra have been observed. The Raman-active Au…Au vibrations of the Me₂Au(OOCR)]₂ molecules were found to be in the same region as those of Me₂AuX]₂. The Au–X stretching modes were observed between 100 and 250 cm⁻¹ in accordance with the DFT predictions. Their frequencies in the IR spectra of Me₂AuX]₂ increase in the sequence I < Br < Cl while the AuC₂ stretching frequencies decrease in the same order. This fact might be an evidence of the decreasing covalent character of the gold-halogen bridges. The Au–O stretching bands of dimethylgold(III) carboxylates have been observed in the 500–250 cm⁻¹ region, and Au–C stretching frequencies of both Me₂AuX]₂ and Me₂Au(OOCR)]₂ compounds have been found between 600 and 500 cm⁻¹.