Novel solvates in AgX:dpex (n:1) systems (n = 1 or 2); X = oxyanion; dppx = Ph2P(Y)PPh2, Y = (CH2)3, Fc

Novel solvated forms are spectroscopically (1H, 13C, 31P, IR and conductivity studies) and structurally described for diverse silver oxyanion salt:bis(diphenylphosphino)-ligand adducts of 2:1:n (AgX:dppx:S) stoichiometry. AgClO4:dppf:MeCN (2:1:4) (‘dppf’ = bis(diphenylphosphino)ferrocene) is a binuclear centrosymmetric species: [(O3ClO )(MeCN )2Ag(P -dppf-P ′)Ag(N CMe)2(O ClO3)], Ag–P short at 2.368(1) Å. Two MeOH/H2O solvates are described, of AgX:dppp (2:1) stoichiometry, both single stranded polymers (X = carboxylate: ‘ac’ = acetate, ‘tfa’ = trifluoroacetate; ‘dppp’ = Ph2P(CH2)xPPh2; x = 3), with silver atoms spanned alternately by: (i) a P -dppp-P ′ bridge, supported by tenuously bridging water or methanol, and (ii) O -ac, tfa-O ′ bridge(s), being assigned stoichiometries Agtfa:dppp:H2O (2:1:1) · MeOH and View the MathML sourceAgac:dppp:MeOH(2:1:0.5)·312H2O. The structure of AgClO4:dppe:MeCN (1:1:1) (‘dppe’, x = 2), also a one-dimensional polymer, but with all Ag…Ag sequences bridged by the P,P′ ligand, and with unidentate MeCN and OClO3 coordinated to the silver, is also recorded.