Comparative DFT study of the effectiveness of p-phenylenediamine antioxidants through their coordination ability towards the late 1st row transition metals. (January 2021)

• Record Type: Journal Article
• Authors: Jelemenská, Ingrid; Breza, Martin
• Is Part Of: Polymer degradation and stability. Volume 183(2021)
• Publication Date: 2021-01
• Subjects: B3LYP functional -- geometry optimization -- population analysis -- topological analysis of electron density -- Molar Antioxidant Effectiveness; Polymers -- Deterioration -- Periodicals; Stabilizing agents -- Periodicals; Polymères -- Dégradation -- Périodiques; Stabilisants -- Périodiques; 668.9
• DOI: 10.1016/j.polymdegradstab.2020.109438
• Languages: English
• ISSNs: 0141-3910

Abstract

Highlights: Geometry optimization of antioxidants and of their transition metal complexes Elimination of complexes without exclusive metal – nitrogen bonds Interaction energy Eint evaluation Population analysis and topological analysis of electron density Similar trends for antiox. effectiveness vs Eint and el. density transfer Abstract: Interaction energies, metal atom charges and electron density Laplacians at bond critical points of metal – nitrogen bonds in [Aox…M] 2+ complexes of a series of p-phenylenediamine antioxidants (Aox) with the late 1 st row transition metals M(II) in various spin states were evaluated in order to predict the antioxidant effectiveness through their coordination ability. The complexes without exclusive metal – nitrogen bonding were excluded. All the above M 2+ dications exhibit similar trends of antioxidant effectiveness relation vs. interaction energies and nitrogen-to-metal electron density transfer. The only problem is in their ability of metal – nitrogen bonding because they are strongly attracted by neighboring aromatic rings. Only copper atoms are bonded exclusively to nitrogens in all the systems under study.