Synthesis and spectroscopic characterization (IR, 1H and 31P NMR, electrospray ionization mass) of mono-, di-, tetra- and poly-meric complexes of silver(I) with diphosphine ligands:: X-ray crystal structures of AgNO2:(Ph2PCH2PPh2) (1:1)2, AgNO2:(Ph2P(CH2)3PPh2) (1:1)2, AgNO2:(Ph2PCH=CHPPh2) (2:1)2 and AgNO2:{p-tolyl)2P(C10H6)2P(p-tolyl)2} (1:1)

Adducts of diphosphine ligands R2P(R')(n)PR2 (dppm: R = Ph, R' = CH2, n = 1; dppe: R = Ph, R' = CH2, n = 2; dppp: R = Ph, R' = CH2, n = 3; dppb: R = Ph, R' = CH2, n = 4; dppf: R = Ph, R' = ferrocenyl, n = 1; dppet: R = Ph, R' = CH=CH, n = 1 dcpm: R = cy, R' = CH2, n = 1; S-Binap: R = Ph, R' = (S)-(+)-1,1-binaphthyl, n = 1, n = 2; (R-Tol-Binap: R = p-tolyl; R' = (R)-(+)-1, 1-binaphthyl, n = 1; (S,S-Diop: R - Ph, R' = (4S,5S-(+)-O-isopropylideile-2-3-dihydroxybutane, n = 1) with silver(I) nitrite have been synthesized and characterized both in solution (H-1, P-31 NMR, ESI MS) and in the solid state (IR, single crystal X-ray structure analysis, P-31 NMR). The topologies of the structures in the solid state were found to depend oil the nature of the diphosphine and ill some cases also oil the stoichiometric ratio AgNO2:R2P(R')(n)PR2. The adducts AgNO2:dppm (1:1)(2) and AgNO2:dppp (1:1)(2) are dimers, the role of dppm and dppp being to bridge two silver centers with each nitrite O,O'-chelating. The adduct AgNO2:dppet (2:1)(2) is tetranuclear, derivative of the chair form, the bidentate ligands bridging central and peripheral silver centers, the nitrite being coordinated through both oxygens, the first unidentate, the second bridging bidentate. R-Tol-Binap forms a mollonuclear 1:1 adduct, with the nitrite all O,O'-chelate. (C) 2003 Elsevier B.V. All rights reserved.