Complexation of [ω-diphenylphosphinoalkyl]diphenylphosphine sulphides with AgNO3

Article abstract of DOI:10.1016/S0022-328X(96)06956-2

By reaction of [ωdiphenylphosphinoalkyl]diphenylphosphine sulphides Ph₂P(CH₂)_nP(S)Ph₂ (n = 2-4) (L¹-L³) with AgNO₃ in CH₃CN crystalline complexes with the composition metal:ligand 1:1 [Ag(L¹)NO₃, Ag(L²)NO₃, Ag(L³)NO₃] and 1:2 [Ag(L¹)₂NO₃, Ag(L³)₂NO₃] were isolated. According to the X-ray analysis data, the crystals of Ag(L¹)NO₃ are constructed from centrosymmetric dimeric molecules based on the 12-membered macrocycle AgSPCH₂CH₂PAgSPCH₂CH₂P. Each of the neutral ligands L¹ is a bridge between two silver ions and each of the silver ions is coordinated by a chelating NO₃ group. According to the IR spectra, the other 1:1 complexes also have an analogous structure. In the 1:2 complexes the coordinated NO₃, groups of the 1:1 complexes are replaced by the phosphine sulphide ligand. The downfield shifts of the signals of P^III and P^v atoms in ³¹P NMR spectra of 1:2 complexes in comparison with the free ligands L¹ and L³ reflect a participation of the P^III atom and P=S group in complex formation.