The structural definition of adducts of stoichiometry MX:dpex (2:3) (∞), M = Cu I, Ag I, X = simple anion, dpex = Ph 2E(CH 2) xEPh 2, E = P, As

Abstract

Single crystal X-ray structural characterizations are recorded for a number of adducts of MX:dpex (2:3) stoichiometry (MX = simple univalent copper or silver salt; dpex = Ph 2E(CH 2) x EPh 2 (E = P, As)). CuX:dppe (2:3) (X = Cl, Br, I, CN) are binuclear [(dppe- P, P′)CuX( P-dppe- P′)CuX( P, P′-dppe)], all centrosymmetric. AgX:dpex (2:3) (dpex = ‘dpae’ (Ph 2As(CH 2) 2AsPh 2), X = Br, F 3CCO 2 (= ‘tfa’), F 3CSO 3 (≡ ‘tfs’); dpex = ‘dpape’ (Ph 2As(CH 2) 2PPh 2), X = CN, SCN, OClO 3) are one-dimensional polymers ⋯– E′) 1AgX( E-dpex- E′) 2-AgX( E-dpex- E′) 1AgX⋯, P, As sites scrambled in the latter. AgNO 3:dpam (2:3) is also a one-dimensional polymer, ⋯Ag O·NO· OAg( As-dpam- As)Ag O·NO· OAg⋯ (‘dpam’ ≡ Ph 2As(CH 2) 2AsPh 2). AgX:dpae (2:3) (X = I, CN, ClO 4, NO 3) and AgX:dpape (2:3) (X = Br, I, NO 3) are two-dimensional polymers with large 30-membered macrocyclic rings; similar webs are found for dppx ligands in AgOH:dppb (2:3) and AgNCO, Agtfa:dpph (2:3) with 42- and 54-membered rings. Complexes AgX:dpape (1:3) (X = Cl, Br) are defined as mono-nuclear [XAg(Ph 2 P(CH 2) 2AsPh 2) 3] arrays, the unidentate ligands predominantly P-bound. Synthetic procedures for the adducts are reported, selected compounds being characterized both in solution ( 1H, 31P NMR, ESI MS) and in the solid state (IR).