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Title of Journal: Theor Chem Acc

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Abbravation: Theoretical Chemistry Accounts

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Springer-Verlag

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10.1016/j.ajo.2004.04.047

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1432-2234

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Oxidation states atomic charges and orbital popul

Authors: Gabriel Aullón Santiago Alvarez
Publish Date: 2009/03/06
Volume: 123, Issue: 1-2, Pages: 67-73
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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 fourcoordinate 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 chargesFinancial support to this work was provided by the Dirección General de Investigación Científica MICINN through grant CTQ200508123C0202/BQU and by Comissionat per a Universitats i Recerca Generalitat de Catalunya grant 2005SGR0036 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 workUnrestricted 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 LeeYangParr correlation functional 23 An allelectron tripleζ 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 CuIIIL43+ L = He NH3 PH3 AsH3 SbH3 CuIIIX4− X = H CF3 CH3 SiH3 SnH3 F Cl Br I OH SH and SeH CuIIL42+ L = He NH3 and PH3 CuIIX42− X = H CF3 and Cl CuIL4+ L = He NH3 and PH3 CuIX43− X = H CF3 ScF4− TiF4 VF4+ VOF3 CrO2F2 MnO3F VO43− CrO42− and MnO4− The geometries of all Cu complexes were verified to correspond to minima in the potential energy surface through vibrational analyses The CuIX43− 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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