Structural, theoretical and multinuclear NMR study of mercury(II) and silver(I) complexes with two new ambidentate phosphorus ylides

► Synthesis and characterization of Ag(I) and Hg(II) complexes of phosphorus ylides. ► X-ray analysis reveals slightly distorted linear structure for Ag(I) complexes. ► Good agreement of bond lengths and angels in theory and experiment. ► The shape of the HOMO-11 can be associated with the Ylide → Ag σ donation.