New silver(I) complexes have been synthesised from the reaction of AgNO3, monodentate PR3 (PR3 = P(o-tolyl)3, P(m-tolyl)3, P(ptolyl) 3, P(p-C6H4F), SeP(C6H5)3) or bidentate tertiary (dppe = bis(diphenylphosphane)ethane, dppf = 1,10-bis(diphenylphosphane)ferrocene) phosphanes and potassium dihydrobis(3-nitro-1,2,4-triazolyl)borate, K[H2B(tzNO2)2]. These compounds have been characterized by elemental analyses, FT-IR, ESI-MS and multinuclear (1H and 31P) NMR spectral data. The adduct {[H2B(tzNO2)2]Ag[P(m-tolyl)3]2} has been characterized by single crystal X-ray studies. In the former, the H2B(tzNO2)2 acts as a monodentate ligand utilizing the coordinating capability of only one of the additional (exo-) ring nitrogens to complete the coordination array about the silver atom.