Two new aminocyclophosphazene complexes of silver(Ⅰ), AgClO_4,N_3P_3(NMe_2)_6 (1) and AgClO_4,2N_3P_3(NMe_2)_6 (2), have been prepared and characterised. Conductimetric evidence shows that the species are complex salts, Ag{N_3P_3(NMe_2)_6}_n~+ClO_4~-, (n = 1 or 2). The ~1Hn.m.r. spectra of the complexes showed the occurrence of long-range differential ~5J(PH) phosphorus proton spin-spin coupling. The ~5J′(PH) and ~5J″(PH) coupling constants have been evaluated and used as indicator of the metal complexation to the aminophosphazene ring. Low temperature ~(31)P n.m.r. spectra show an A2B type spin system for the adducts. The bonding mode has been discussed; existence of σ-π rearrangement is postulated in the Ag-aminophosphazene linkage. The i.r. spectra give evidence for the existence of bidentate perchlorate bridging, -OCl(O_2)O-, between the silver nuclei in the solid state.
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