Bond Stretching and Redox Behavior in Coinage Metal Complexes of the Dichalcogenide Dianions [(SPh2P)2CEEC(PPh2S)2]2− (E=S, Se): Diradical Character of the Dinuclear Copper(I) Complex (E=S)

The metathetical reactions of a) [Li(tmeda)]2[(S)C(PPh2S)2] (Li2⋅3 c) with CuCl2 and b) [Li(tmeda)]2[(SPh2P)2CSSC(PPh2S)2] (Li2⋅4 c) with two equivalents of CuCl both afford the binuclear CuI complex {Cu2[(SPh2P)2CSSC(PPh2S)2]} (5 c). The elongated (C)S[BOND]S(C) bond (ca. 2.54 and 2.72 Å) of the dianionic ligand observed in the solid-state structure of 5 c indicate the presence of diradical character as supported by theoretical analyses. The treatment of [Li(tmeda)]2[(SPh2P)2CSeSeC(PPh2S)2] (Li2⋅4 b) and Li2⋅4 c with AgOSO2CF3 produce the analogous AgI derivatives, {Ag2[(SPh2P)2CEEC(PPh2S)2]} (6 b, E=Se; 6 c, E=S), respectively. The diselenide complex 6 b exhibits notably weaker Ag[BOND]Se(C) bonds than the corresponding contacts in the CuI congeners, and the 31P NMR data suggest a possible isomerization in solution. In contrast to the metathesis observed for CuI and AgI reagents, the reactions of Li2⋅4 b and Li2⋅4 c with Au(CO)Cl involve a redox process in which the dimeric dichalcogenide ligands are reduced to the corresponding monomeric dianions, [(E)C(PPh2S)2]2− (3 b, E=Se; 3 c, E=S), and one of the gold centers is oxidized to generate the mixed-valent AuI/AuIII complexes, {Au[(E)C(PPh2S)2]}2 (7 b, E=Se; 7 c, E=S), with relatively strong aurophilic AuI⋅⋅⋅AuIII interactions. The new compounds 5 c, 6 b,c and 7 b,c are characterized in solution by NMR spectroscopy and in the solid state by X-ray crystallography (5 c, 6 b, 7 b and 7 c) and by Raman spectroscopy (5 c and 6 c). The UV-visible spectra of coinage metal complexes of the type 5, 6 and 7 are discussed in the light of results from theoretical analyses using time-dependent density functional theory.peerReviewe