Synthesis and structural characterisation of four 1:1:2 ionic/mononuclear complexes of Ag(I) and Cu(I) salts with tertiary organophosphine and 1,2-diamines.

[Display omitted] • Synthesis of coinage metal complexes in 1,2-diamines as solvent. • 1:1:2 ionic/mononuclear complexes of silver and copper with triphenylphosphine and 1,2 diamine ligands. • Structure determination of mixed-ligands Cu(I) and Ag(I) complexes shows two crystallographically independent cations which are conformationally different. Crystallization of copper(I) halide : triphenylphosphine mixtures from 1,2-diaminoethane (en = ethylenediamine) has yielded adducts 1:1:2 CuX:PPh 3 :en stoichiometry (X = Cl or I); the chloride and iodide have been characterized by room temperature single crystal X-ray structure determinations; the iodide is a hemisolvate. In both cases, the complex is ionic, the four coordinate CuPN 3 environment comprising both bidentate and unidentate en, i.e [(κ2- N,N' -en)(κ1- N -en)(PPh 3)Cu]+X−. In each case, there are two crystallographically independent cations which are conformationally different. Adduct [(PPh 3)(κ 2- N,N' -en)(κ 1- N -en)Cu]Cl is very unstable and decomposes on air, whereas [(κ 2- N,N' -en)(κ 1- N -en)(PPh 3)Cu]I is sufficiently stable both in the solid state and in solution to be characterized. Adducts of similar stoichiometry are obtained with silver(I) nitrate, and with silver(I) perchlorate with PCy 3 , and 1,2-diaminopropane (pn): the single crystal X-ray structure determinations confirm the ionic/mononuclear formulations [(κ2- N,N' -en)(κ1- N -en)(PPh 3)Ag]NO 3 and [(κ2- N,N' -en)(κ1- N -en)(PCy 3)Ag]ClO 4 that persist also in acetonitrile, as confirmed by conductance values typical of 1:1 electrolytes in this solvent. [ABSTRACT FROM AUTHOR]