Abstract
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 (1H and 31P) 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)}]2·2CHCl3, [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.
Published Version
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