New silver(i) complexes have been synthesized from the reaction of AgNO3, monodentate tertiary phosphanes PR3 (PR3 = P(C6H5)3, P(o-C6H4CH3)3, P(m-C6H4CH3)3, P(p-C6H4CH3)3, PCH3(C6H5)2) and two novel electron withdrawing ligands: potassium dihydrobis(3-nitropyrazol-1-yl)borate and potassium dihydrobis(3-trifluoromethylpyrazol-1-yl)borate. These compounds have been characterized by elemental analyses, FT-IR, ESI-MS and multinuclear (¹H, ¹⁹F and ³¹P) NMR spectroscopy. Solid state structures of the potassium salts K[H2B(3-(NO2)pz)2] and K[H2B(3-(CF3)pz)2] have been reported. They form polymeric networks due to intermolecular contacts of various types between the potassium ion and atoms of the neighboring molecules. The silver adducts [H2B(3-(NO2)pz)2]Ag[P(C6H5)3]2 and [H2B(3-(NO2)pz)2]Ag[P(p-C6H4CH3)3] have pseudo tetrahedral and trigonal planar silver sites, respectively. The bis(pyrazolyl)borate ligand acts as a κ²-N2 donor. The nitro-substituents are coplanar with the pyrazolyl rings in all these adducts indicating efficient electron delocalization between the two units. The [H2B(3-(CF3)pz)2]Ag[P(C6H5)3] complex has been obtained from re-crystallization of {[H2B(3-(CF3)pz)2]Ag[P(C6H5)3]2} in a dichloromethaneâ diethyl ether solution; it is a three-coordinate, trigonal planar silver complex.