Abstract
Exposure of salts and aqueous glasses containing tetracyanonickelate(II) ions to 60Co γ-rays at 77 K gives [Ni(CN)4]3–(d9) and [Ni(CN)4]–(d7) ions, identified by their g-tensor components, which are markedly dependent upon the medium. For the d9 complexes this dependence is assigned to interaction with the cyanide ligands, and for the d7 complexes to interactions in the axial sites. The former ions have a…d1x2–y2 configuration, and the latter a …d1z2 configuration on nickel. In the potassium salt, and in aqueous glasses containing methanol, d7 centres are formed whose e.s.r. spectra exhibit large hyperfine coupling to one 14N nucleus. In certain cases, especially for the barium salt, a novel species exhibiting large hyperfine coupling (ca. 150 G) to a single proton has been detected. This is identified as the complex [HNi(CN)4]2–.
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