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

Abstract

New silver (I) derivatives containing monodentate tertiary phosphanes and anionic poly(triazol-1-yl)borate ligands have been prepared from the reaction of AgNO 3 and PR 3 (R = Ph, Bn, o-tolyl, m-tolyl, p-tolyl) and potassium dihydrobis(1,2,4-triazolyl)borate, K[H 2B(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 [{H 2B(tz) 2}Ag(PR 3) 2] into [{H 2B(tz) 2}Ag(PR 3)] and PR 3. All the compounds are soluble in chlorinated solvents and are non-electrolytes in CH 2Cl 2 and acetone solutions. [{H 2B(tz) 2}Ag(PPh 3) 2] and [{H 2B(tz) 2}Ag{P( m-tolyl) 3} 2] are simple mononuclear arrays, the silver atoms lying in four-coordinate N 2AgP 2 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 [{H 2B(tz) 2}Ag{P( p-tolyl) 3}], the silver environment is still four-coordinate but PAgN 3, 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.