Bonding properties of halide transition metal (ii) complexes of glyoxime ligand: DFT; QTAIM; EDA and CDA studies Djendo Mazia Suzane Leonie, Ndom Jean Claude, Bikele Mama Désiré Department of Chemistry, Faculty of Science, University of Douala, Douala, Cameroon Our investigation has been focused on the bonding properties of halide transition metal (II) complexes of glyoxime ligand using a series of computational tools ((quantum theory of atoms in molecules (QTAIM), Energy decomposition Analysis (EDA) and Charge decomposition Analysis (CDA)) from optimized structures at B3LYP/GEN (GEN: LanL2DZ for nd x (x= 6,7 and 8) transition metals (also for halogen atoms (Br and Cl)) and polarized and diffuse triple Pople basis set (6-311++G(d,p)). The topological examination (QTAIM) indicates the intermediate nature of the metal-ligand interactions (partially covalent bond) in our two study media (gas and aqueous). The bonding energies estimated ranging from 3 to 10 kcal/mol reveal the van der Waal type of all the interactions. In the whole, the binding strength has shown to depend on the nature of the halogen, the multiplicity adopted and the study medium. The Energy decomposition Analysis (EDA) illustrates the electrostatic interaction strength appears to be preponderant within the chloride nd 7 and nd 8 transition metal complexes. A poor coordination of bromide ligand to the central metal has also been observed at the lower spin state. The growth of the [glyoxime ligand]→ [Metal (halogen atom) 2 ] interaction strength detected by the EDA is in the following order: Fe 2+ <Co 2+ <Ni 2+ (3d) , Pd 2+ <Rh 2+ <Ru 2+ (4d) and Pt 2+ <Ir 2+ <Os 2+ (5d). We have also detected that these interaction strengths in a column of the periodic table tend to increase from the top to the bottom in both series regardless of the environment. In the whole, the higher back donation factor (EDA) reflects the low formation barrier of the chloride complexes in the gas phase and their bromide counterparts in water. For this last sequence, an exception is observed for the bromide platinum complex. The total energy of each complex formed in various states the negative value of energy difference indicating higher stability. Keywords: Dihalogenoglyoxime ligands, DFT; QTAIM, EDA and CDA References 1. B. Yildirim., E.Özcan, P. Deveci,. Russian Journal of Coordination Chemistry, Vol. 33, No. 6, (2007) 417–421. b) L. Minglian et al. Journal of theoretical and computational chemistry (2011) 861-874. 2. Ł.Orzeł, J. Was, A. Kania, A. Susz, D. Rutkowska‑Zbik, J. Staron, M. Witko, G. Stochel, L.Fiedor. Factors controlling the reactivity of divalent metal ions towards pheophytin a. J.Biol Inorg. Chem. ( 2017 ) 941–952. 3. G. Frenking, Miquel Sola, Sergei F. Vyboishchikov. Chemical bonding in transition metal carbene complexes, Journal of Organometallic Chemistry 690 (2005) 6178–6204 4. Jagadeesan R, Velmurugan G, Venuvanalingam P RSC Adv 5 (2015) 80661–80667.
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