Abstract
Quantum-chemical calculations have been performed by an iterative extended Hückel method to examine the electronic structures for chlorhemin and the product from its interaction with aniline, while an interpretation is also given of data obtained previously by 57Fe Mössbauer spectroscopy. The results indicate that chlorhemin reacts with aniline to give low-spin six-coordinated ferriporphyrins (hemochromes). The quadrupole splittings ΔEQ and the s-electron densities at the 57Fe nuclei have been calculated for bis-aniline hemochrome and hemin, as these determine the isomeric shifts. Two forms of calculation are compared with experiment: from the use of one-term functions of Slater type for the Fe AO and by the use of multiexponential expansions. Modified calculations have been performed on the isomeric shifts in the complete bases of all the Fe AO, which enables one to eliminate the usual procedure for orthogonizing the core s electrons. The MO have been classified and the orbital interactions have been analyzed for both compounds.
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Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 22, No. 5, pp. 553–562, September–October 1986.
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Burykin, B.N., Khleskov, V.I. & Garibov, R.É. Quantum-chemical study of the electronic structure of the aniline-hemin complex: Mössbauer parameter interpretation. Theor Exp Chem 22, 527–534 (1987). https://doi.org/10.1007/BF00522537
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DOI: https://doi.org/10.1007/BF00522537