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Eloy Ramos-Cordoba, Marc Garcia-Borràs, and Pedro Salvador
Institut de Química Computacional I catàlisi (IQCC) I Departament de Química, Universitat de Girona, Facultat de Ciències,
Campus Montilivi s/n, 17071 Girona, Spain.
email: [email protected]
The concept of oxidation state (OS) is widespread in transition metal chemistry and in the study of redox and catalytic
reactions. The reactivity, spin-state, spectroscopic and geometrical features of transition metal (TM) complexes are often
rationalized on the basis of the OS of the metal center. OS are intrinsically related to the electronic distribution, but
electronic or spin populations are only a pointer of the atom's OS. We have most recently shown that the so-called effective
atomic orbitals (eff-AO's) can be utilized, treating alpha and beta electrons separately, to derive the most appropriate
atomic electron configurations for the atoms or molecular fragments in the molecule. Accordingly, we have introduced a
simple and general way to derive effective oxidation states (EOS) from the analysis of the electron density/wavefunction.
The method is general and it can formally be applied to any molecular system but the focus is on transition metal and
organometallic chemistry for which the concept of the OS is most relevant. For practical applications we have proposed a
hierarchical strategy based on the partitioning of the molecular system into fragment/ligands prior to the eff-AO analysis. In
this study we have applied the EOS to a series of endohedral metallofulerenes (EMFs) ranging from trimetallic nitride
templates (TNT) to metallic carbides.
E. Ramos-Cordoba, P. Salvador, Oxidation states from wavefunction analysis, submitted for publication
E. Ramos-Cordoba, P. Salvador, I. Mayer, J. Chem. Phys., 138, 214107 (2013)