Silver (I) poly(1,2,4-triazolyl)borate complexes containing monodentate phosphane ligands

New silver (I) derivatives containing monodentate tertiary phosphanes and anionic poly(triazol-1-yl)borate ligands have been prepared from the reaction of AgNO3 and PR3 (R = Ph, Bn, o-tolyl, m-tolyl, p-tolyl) and potassium dihydrobis(1,2,4-triazolyl)borate, K[H2B(tz)2], or potassium hydrotris(1,2,4-triazolyl)borate, K[HB(tz)3]; their solid state and solution properties have been investigated through analytical and spectroscopic measurements (IR, 1H-, and 31P NMR). The 1H- and 31P NMR solution spectra in some cases can be interpreted on the basis of a dissociation of [{H2B(tz)2}Ag(PR3)2] into [{H2B(tz)2}Ag(PR3)] and PR3. All the compounds are soluble in chlorinated solvents and are non-electrolytes in CH2Cl2 and acetone solutions. [{H2B(tz)2}Ag(PPh3)2] and [{H2B(tz)2}Ag{P(m-tolyl)3}2] are simple mononuclear arrays, the silver atoms lying in four-coordinate N2AgP2 environments. Owing to the presence of the methyl substituents on the phosphane ligand, the complex [{HB(tz)3}Ag{P(o-tolyl)3}], as expected, is mononuclear. In [{H2B(tz)2}Ag{P(p-tolyl)3}], the silver environment is still four-coordinate but PAgN3, utilizing the coordinating capability of one of the additional (‘exo’-) ring nitrogens not only to complete the four-coordinate array about the silver but, necessarily, to link successive asymmetric units into a single-stranded polymer.