First heterobimetallic AgI-CoIII coordination compound with both bridging and terminal -NO2 coordination modes: synthesis, characterization, structural and computational studies of (PPh3)2AgI-(µ-κ2O,O':κN-NO2)-CoIII(DMGH)2(κN-NO2).

An unusual heterobimetallic bis(triphenylphosphane)(NO2)AgI-CoIII(dimethylglyoximate)(NO2) coordination compound with both bridging and terminal -NO2 (nitro) coordination modes has been isolated and characterized from the reaction of [CoCl(DMGH)2(PPh3)] (DMGH2 is dimethylglyoxime or N,N'-dihydroxybutane-2,3-diimine) with excess AgNO2. In the title compound, namely bis(dimethylglyoximato-1κ2O,O')(µ-nitro-1κN:2κ2O,O')(nitro-1κN)bis(triphenylphosphane-2κP)cobalt(III)silver(I), [AgCo(C4H7N2O2)2(NO2)2(C18H15P)2], one of the ambidentate -NO2 ligands, in a bridging mode, chelates the AgI atom in an isobidentate κ2O,O'-manner and its N atom is coordinated to the CoIII atom. The other -NO2 ligand is terminally κN-coordinated to the CoIII atom. The structure has been fully characterized by X-ray crystallography and spectroscopic methods. Density functional theory (DFT) and time-dependent density functional theory (TD-DFT) have been used to study the ground-state electronic structure and elucidate the origin of the electronic transitions, respectively.