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Ultraviolet Absorption Spectra and the Electronic Structure of Metallic Complexes. II. Cyanide Complexes

1958; Oxford University Press; Volume: 31; Issue: 1 Linguagem: Inglês

10.1246/bcsj.31.79

1348-0634

Sigeo Kida, Junnosuke Fujita, Kazuo Nakamoto, Ryutaro Tsuchida,

Photochemistry and Electron Transfer Studies

Abstract The energy levels of the cyanide complexes–hexacyano chromium (III) [Cr(CN)6]3−, hexacyno cobalt (III) [Co(CN)6]3−, tetracyano nickel(II) [Ni(CN)4]2−, and tetracyano copper (I) [Cu(CN)4]3 ions have been calculated by the semi-emprical M.O. method taking π-orbitals of the ligands into consideration. The ionization potentials used have been determined so that the calculated charge distribution does not contradict that obtained from Pauling’s neutrality principle. The stability and the magnetic property of these complexes have been well interpreted by our calculation. The results have revealed that the first and the second bands of hexacyano chromium (III) [Co(CN)6]3− and hexacyano cobalt (III) [Co(CN)6]3− are attributable to f′2g→ e′g transitions which are of the similar character to the first and the second bands of hexammine cobalt (III) [Co(NH3)6]3+, although the ground level, f′2g combines strongly with the π-orbitals of the ligands. In tetracyano nickel(II) [Ni(CN)4]2−, the “second band” is hidden by the allowed transition. For tetracyano copper (I) [Cu(CN)4]3−, there is no band corresponding to “the first and the second band”.