A neutral vicinal silylene/phosphane supported six-membered C₂PSiAu₂ ring and a silver(i) complex

This work presents the different coordination nature of the bidentate ligand towards gold and silver complexes. The reaction of 1 with AuClSMe₂ in dichloromethane resulted in two gold atoms containing six-membered ring PhC(N^tBu)₂Si-Au⋯Au-PPh₂C₆H₄ (2). Compound 2 exhibits intramolecular aurophilic interaction (2.9987(7) Å), which is further supported by quantum chemical calculations. Moreover, the reduction of aluminium adduct 3 with AgSbF₆ affords insertion of silver cation [{PhC(N^tBu)₂SiF₂}-C₆H₄(PPh₂)-Ag-(PPh₂)C₆H₄{PhC(N^tBu)₂SiF₂}]AlCl₄⁻ (4) between two phosphane. In compound 4 only two P(iii) of two molecules of 1 coordinates to Ag(i), while two Si(ii) remains uncoordinated and gives oxidative addition of Fluorine.