Synthesis and structural characterization of adducts of silver(I) oxyanion salts, AgX (X = ClO4, NO3), with Ph2E(CH2)xEPh2 (‘dpex’; E = P, As; x = 1–4) and oligodentate aromatic N-bases derivative of 2,2′-bipyridyl, ‘L’, AgX:dpex:L (2:1:2)

The syntheses and the spectroscopic characterization (IR, 1H, 13C and 31P NMR, ESI-MS and conductivity studies) of a number of adducts of silver(I) perchlorate and nitrate, AgX, with N,N′(,N″)-oligodentate ligands L, derivative of 2,2′-bipyridyl, together with Ph2E(CH2)xEPh2 (≡‘dpex’, x predominantly 1,2 (‘dpem’, ‘dpee’) but also 3,4 (‘dppp’, ‘dppb’), E = P, As) are reported, of stoichiometry AgX:dpex:L (2:1:2), L = 2,2′-bipyridyl (‘bpy’); 1,10-phenanthroline (‘phen’); 2,9-dimethyl, 1,10-phenanthroline (‘dmp’); bis(2-pyridyl)amine (‘dpa’); 2,2′-biquinolyl (‘bq’); 2,2′:6′,2″-terpyridyl (‘tpy’). For AgClO4:dppm:bpy, phen, dmp, tpy; AgClO4:dpem:phen, dmp, tpy; AgNO3:dppm:bpy, bq (2:1:2), the compounds are of the form [LAg(E-dpem-E′)AgL]X2, the pair of Ag–E bonds lying cis/parallel about the ECH2E core, of quasi-C2v symmetry; for AgClO4:dppm:dpa; AgNO3:dppm:bpy (2:1:2), the Ag–E bonds lie trans, with a cation symmetry (quasi-)2. In AgNO3:dppm, dpam:dmp (2:1:2), loosely coordinated nitrate ions approach one of the silver atoms as unidentate ligands, Ag–E being ‘cis’: [(O2NO)(dmp)Ag(E-dpem-E′)Ag(dpm)](NO3). The majority of [LAg(E-dpex-E′)AgL] (dpex = dpee, dpeb) arrays (AgClO4:dppe:bpy, bq, dpa, tmp, tpy; AgClO4:dpae:bpy, bq; AgClO4:dpdae:dmp (E = P, E′ = As); AgClO4:dppb:dpa, bq, tpy; AgNO3:dppb:tpy (2:1:2)) are centrosymmetric and trans-oid with close approaches to the silver atoms by oxyanions or solvent (MeCN) molecules; AgClO4:dpae:dmp (2:1:2) is cis-oid, as also are the dppp adducts, AgClO4:dppp:dmp, bq (2:1:2). A novel bridging tpy coordination mode is found, whereby pairs of silver atoms are linked η2 (σ, π) into a single stranded polymer in AgClO4:dppp:tpy (2:1:2), thus […Ag(P-dppp-P′)Ag((μ-N″)tpy)2…](∞|∞).

Graphical abstractSilver(I) perchlorate and nitrate, AgX, with N,N′(,N″)-oligodentate ligands L, derivative of 2,2′-bipyridyl, together with Ph2E(CH2)xEPh2 are reported, of stoichiometry AgX:dpex:L (2:1:2). For AgClO4:dppm:bpy, phen, dmp, tpy; AgClO4:dpem:phen, dmp, tpy; AgNO3:dppm:bpy, bq (2:1:2), the compounds are of the form [LAg(E-dpem-E′)AgL]X2.Figure optionsDownload full-size imageDownload as PowerPoint slide