The study of transition-metal complexes with ethylenediamine and cyano ligands by means of the X-ray photoelectron spectra.

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The X-ray photoelectron spectra (XPS) were measured in order to obtain the Nls and Cls core-orbital energies of ten ethylenediamine and 21 cyano complexes of transition metals. The difference between the Nls and Cls energies, ΔE, which was found to be hardly affected by the counter ion or by charging, was accurately determined for each complex. The trends observed in the ΔE values for these series of complexes are correlated with the electronic structures of the complexes by the use of Siegbahn's equation. For the ethylenediamine complexes, the ΔE values are shown to be related to the σ donation. For the cyano complexes, the ΔE values are mainly controlled by the nitrogen charge, which is itself closely connected with the π back-donation. Demonstrative of the importance of the π back-donation are the cases of [Fe(CN)6]4− and [Fe(CN)6]3−, where the decrease in the negative charge from the former to the latter is found to occur dominantly (76%) in the nitrogen atoms. Molecular orbital (MO) calculations in the discrete variational Xα (DV-Xα) scheme were performed for a few series of the cyano complexes, giving results consistent with the XPS results.
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