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Oxidation states, atomic charges and orbital populations in transition metal complexes

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Abstract

The differences and similarities between calculated atomic charge and formal oxidation state in transition metal complexes are discussed in the light of density functional theory calculations on a variety of four-coordinate complexes. It is shown that the oxidation state formalism provides a framework for the classification of families of compounds related by ligand substitution or redox processes, and can neither be replaced by nor deduced from net atomic charges.

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Notes

  1. In Pauling’s words: “In a covalent compound of known structure, the oxidation number of each atom is the charge remaining on the atom when each shared electron pair is assigned completely to the more electronegative of the two atoms sharing it” [8].

  2. A significant example of an inverted ligand field was found in band electronic structure calculations of the LaFe4P12 skutterudite, which showed that the Fermi level has more phosphorus than Fe 3d character, and lead to the conclusion that its superconductivity is associated with the phosphorus sublattice rather than with the iron atoms [18].

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Acknowledgments

Financial support to this work was provided by the Dirección General de Investigación Científica (MICINN) through grant CTQ2005-08123-C02-02/BQU and by Comissionat per a Universitats i Recerca (Generalitat de Catalunya), grant 2005SGR-0036. The computing resources at the Centre de Supercomputació de Catalunya (CESCA) were made available in part through a grant from Fundació Catalana per a la Recerca (FCR) and Universitat de Barcelona. The authors thank R. Hoffmann and C. Mealli for intense discussions that inspired this work.

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Authors and Affiliations

  1. Departament de Química Inorgànica, Institut de Química Teòrica i Computacional (IQTC), Universitat de Barcelona, Martí i Franquès 1-11, 08028, Barcelona, Spain

    Gabriel Aullón & Santiago Alvarez

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  1. Gabriel Aullón
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  2. Santiago Alvarez
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Correspondence to Santiago Alvarez.

Additional information

Dedicated to Professor Santiago Olivella on the occasion of his 65th birthday and published as part of the Olivella Festschrift Issue.

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Supporting information (DOC 187 kb)

Appendix: Computational details

Appendix: Computational details

Unrestricted density functional calculations were carried out using the GAUSSIAN03 package [21], with the B3LYP hybrid method that employs the Becke three parameters exchange functional [22] and the Lee-Yang-Parr correlation functional [23]. An all-electron triple-ζ basis set was used for all transition metals [24], supplemented with two polarization functions [24, 25]. A basis set of similar quality was used for the main group elements [24], supplemented with extra polarization and diffuse functions, except for the H atoms not bonded to a metal [25]. An effective core pseudopotential was used for I [26] and Sb [27]. The following complexes were fully optimized: [CuIIIL4]3+ (L = He, NH3, PH3, AsH3, SbH3), [CuIIIX4]− (X = H, CF3, CH3, SiH3, SnH3, F, Cl, Br, I, OH, SH and SeH), [CuIIL4]2+ (L = He, NH3 and PH3), [CuIIX4]2− (X = H, CF3 and Cl), [CuIL4]+ (L = He, NH3 and PH3), [CuIX4]3− (X = H, CF3), [ScF4]−, [TiF4], [VF4]+, [VOF3], [CrO2F2], [MnO3F], [VO4]3−, [CrO4]2− and [MnO4]−. The geometries of all Cu complexes were verified to correspond to minima in the potential energy surface through vibrational analyses. The [CuIX4]3− anions (X = F, Cl, Br and I) have not been included in this study because they had been found previously to be unstable toward ligand dissociation [28]. The calculated charges reported were obtained from a natural population analysis [29], but the same qualitative trends were obtained with the atomic polar tensors (APT) method [30] (see Supporting Information).

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Aullón, G., Alvarez, S. Oxidation states, atomic charges and orbital populations in transition metal complexes. Theor Chem Acc 123, 67–73 (2009). https://doi.org/10.1007/s00214-009-0537-9

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