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XPS study of the electronic structure of heterometallic complexes [Fe2MO(O2CCH3)6(H2O)3] · 3H2O (M = Co, Ni)

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Abstract

Heterometallic compounds of general formula [Fe III2 MIIO(O2CR)6(H2O)3] · 3H2O (R = CH3, M = Co, Ni; R = CCl3, M = Co, Ni) have been studied by XPS. The compounds have been identified as high-spin complexes with metal atoms in oxidation states M(II) and M(III). Analysis of the XPS data revealed the tendency of the XPS pattern and magnetic parameters of molecules to change with a change in the electronic nature of metal atoms. The assignment is based on the degree of covalence of the M-O bond. In chloro-substituted heterocomplexes, electron density delocalization on the metal atoms with metal-to-ligand charge transfer through three bonds (M-O-C-C) is observed. The substitution in terminal groups leads to the change in the electron density distribution between the carboxylate and terminal groups.

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Correspondence to T. M. Ivanova.

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Original Russian Text © T.M. Ivanova, K.I. Maslakov, R.V. Linko, I.S. Evstifeev, M.A. Kiskin, I.N. Shcherbakov, S.V. Savilov, V.V. Lunin, V.M. Novotortsev, I.L. Eremenko, 2014, published in Zhurnal Neorganicheskoi Khimii, 2014, Vol. 59, No. 7, pp. 878–886.

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Ivanova, T.M., Maslakov, K.I., Linko, R.V. et al. XPS study of the electronic structure of heterometallic complexes [Fe2MO(O2CCH3)6(H2O)3] · 3H2O (M = Co, Ni). Russ. J. Inorg. Chem. 59, 670–677 (2014). https://doi.org/10.1134/S0036023614070067

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