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The electronic spectra of the hexafluoro complexes of the second and third transition series

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Chemical Bonding in Solids

Part of the book series: Structure and Bonding ((STRUCTURE,volume 19))

Abstract

The present work in conjunction with our earlier (1) treatment of the 3d data constitutes a tolerably complete survey of the electronic spectra of all the transition metal hexafluoro complexes. A number of obvious gaps still remain — for example the neutral hexafluorides (MF6) of the 4d series — and more data for the MF −6 5d series would also be welcome, as would further study of some of the systems here treated. The general trends are however clear and in this respect the study of fluoro species has proved of great value by virtue of the ability of the fluoride ligand to stabilise such a wide range of oxidation states, the higher of which are frequently not accessible in other systems. Some aspects of the interpretation of the spectra still present difficulties, for example the separation of central field and symmetry restricted covalency effects, and in this matter the results of photoelectron spectroscopy and ESCA studies may well prove valuable. Thus, for the MCl 2−6 anions of the 5d series ESCA studies (94) have established that the effective positive charge on the metal decreases from left to right across the series, just as suggested by our interpretation of the spectroscopic data in Table 25. There is however a substantial discrepancy in the magnitudes of the metal positive charges thereby deduced, which clearly renders desirable a reconsideration of the meaning and significance of the z eff parameters customarily used to describe such situations, and further work is in progress directed towards this end.

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Author notes

  1. G. C. Allen

    Present address: Central Electricity Generating Board, Berkeley Nuclear Laboratories, Berkeley, Gloucestershire, England, U. K.

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  1. Department of Chemistry, University College, Cardiff, Wales, U.K.

    G. C. Allen & K. D. Warren

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  1. G. C. Allen
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  2. K. D. Warren
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R. D. Shannon H. Vincent A. Kjekshus T. Rakke G. C. Allen K. D. Warren

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Allen, G.C., Warren, K.D. (1974). The electronic spectra of the hexafluoro complexes of the second and third transition series. In: Shannon, R.D., Vincent, H., Kjekshus, A., Rakke, T., Allen, G.C., Warren, K.D. (eds) Chemical Bonding in Solids. Structure and Bonding, vol 19. Springer, Berlin, Heidelberg. https://doi.org/10.1007/BFb0116570

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  • DOI: https://doi.org/10.1007/BFb0116570

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