A neutral vicinal silylene/phosphane supported six-membered C 2 PSiAu 2 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 AuClSMe 2 in dichloromethane resulted in two gold atoms containing six-membered ring PhC(N t Bu) 2 Si-Au⋯Au-PPh 2 C 6 H 4 (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 AgSbF 6 affords insertion of silver cation [{PhC(N t Bu) 2 SiF 2 }-C 6 H 4 (PPh 2 )-Ag-(PPh 2 )C 6 H 4 {PhC(N t Bu) 2 SiF 2 }]AlCl 4 - (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.