Reactivity and a Charge-Transfer Model Analysis in Aminopolycarboxylic–Metal Complexes

Nawel Redjem (1) , Salima Lakehal (2, 3) , Aicha Lakehal (3) , Christophe Morell (4, 5, 6) , Lynda Merzoud (7) , Henry Chermette (7)

1 Laboratoire de Chimie Appliquée et Technologie des Matériaux
2 Laboratoire de Chimie des Matériaux et des Vivants: Activité & Réactivité
3 Institut des Sciences de la Terre et de l’univers
4 ISA - Institut des Sciences Analytiques
5 ISA-Theoretical chemistry and A.I. - Chimie théorique et Intelligence artificielle
6 UCBL - Université Claude Bernard Lyon 1
7 Chemometrics and theoretical chemistry. - Chimiométrie et chimie théorique

In the present work, we have calculated several DFT reactivity descriptors for the aminopoly carboxylates acids (APCs) at B3LYP/6311++G (d,p) levels of theory aiming to analyze its reactivity. Reactivity descriptors such as ionization energy, molecular hardness, electrophilicity, and condensed Fukui function local indices have been determined to predict the reactivity of APCs. The influence of the solvent was taken into account employing the CPCM model. The results indicate that the solvation slightly modifies the tendency of the reactivity of the APCs studied. On the other hand, we applied a global and local charge transfer partitioning model, which introduces two charge transfer channels (one for accepting electrons (electrophilic) and another for donating one (nucleophilic)), to the complexation reaction of a set of APC acids with transition metals (the Mn, Co and Ni target enlarged by Fe, Cu and Zn). The correlation between the charges obtained for the interaction between APC acids and transition metals stability constants provides support for their interpretation as measures of the electrophilicity and nucleophilicity of a chemical species, and, at the same time, allows one to describe the donation and back-donation processes in terms of the density functional theory of chemical reactivity. Also, the application of dual descriptors for this acids provides valuable information concerning the atoms in the reactants playing the most important roles in the reaction, and thus, helping to improve our understanding of the reaction under study.

Domaines: Chimie

Nawel Redjem, Salima Lakehal, Aicha Lakehal, Christophe Morell, Lynda Merzoud, et al.. Reactivity and a Charge-Transfer Model Analysis in Aminopolycarboxylic–Metal Complexes. Inorganic Chemistry, 2022, 61 (11), pp.4673-4680. ⟨10.1021/acs.inorgchem.1c03860⟩. ⟨hal-04279835⟩