Bridged poly(1-imidazolyl)borate silver(I) complexes containing tertiary mono(phosphine) ligands. The first structurally authenticated bis(imidazolyl)borate metal complex

New silver(I) derivatives containing triorganophosphines and the anionic dihydrobis(1-imidazolyl)borate [H2B(im)(2)](-), or the tetrakis(1-imidazolyl)borate ligand, [B(im)(4)](-), have been synthesized from reaction of AgNO3 with PR3 (R=phenyl, cyclohexyl, o-, m- or p-tolyl) or (PPh2R') (R'=methyl or ethyl) and K{H2B(im)(2)}. DMAC [DMAC=dimethylacetamide) or K[B(im)(4)]. Binuclear [Ag(PR3)(2){(im)BX2(im)}](2) or polymeric [Ag(PR3){(im)BX2(im)}](n) (X=H or imidazolate) complexes have been obtained and fully characterized by elemental analyses and FT-IR in the solid state and by NMR (H-1 and P-31) spectroscopy and conductivity measurements in solution. Solution data are consistent with partial dissociation of complexes, occurring through breaking of both Ag-N and Ag-P bonds. The structures of [Ag{P(C6H4Me-p)(3)}(2){(im)BH2(im)}](2). 2CHCl(3), [Ag{P(cy)(3)}{(im)BH2(im)}](n) and [{P(cy)(3)}Ag{(im)B(im)(2)(im)}](2). MeCN have been determined by single crystal X-ray studies. The [Ag{P(cy)(3)}{(im)BH2(im)}](n) adduct is a single-stranded polymer containing three-coordinate silver atoms (PAgN2 core), while in the two other adducts, the silver atoms are four-coordinate (P2AgN2 cores). In all structures the two silver atoms are bridged by independent imidazolate donors from a pair of (im)BX2(im) moieties.