Silver(I) imidazole perchlorate

The crystal structure of silver(I) imidazole perchlorate reveals the presence of a planar (Ag+)6 cluster, in which three radiating pairs of Ag+ ions 3.051(1) A apart are disposed on the corners of an equilateral triangle, the inner Ag+ ions being 3.493(1) A apart. Each silver ion carries two linearly co-ordinated imidazole ligands, the whole unit has 32 (D3) symmetry. Exposure to 60Co γ-rays at 77 K results in electron addition to a group of three equivalent silver atoms. The 109Ag, 107Ag, and 14N hyperfine coupling constants show that the total 5s character of the unpaired electron is only ca. 0.55, and delocalisation onto six equivalent nitrogen ligands accounts for ca. 0.25. Low g values suggest that the remaining spin density is in 5p orbitals on silver. There is no indication of delocalisation onto the remaining three Ag+ ions in the cluster. Possible reasons for this selectivity are discussed. The electron-loss centre appears to be a normal Ag2+ complex. It is suggested that marked distortion results in the hole being trapped on one silver rather than being delocalised. (author)