Suzane Leonie Djendo Mazia, Moto Ongagna Jean, Adjieufack Abel Idrice, Daniel Lissouck, Jean Claude Ndom, Désiré Bikele Mama
{"title":"低旋和高旋基态对二甲基乙二醛肟配体与二卤过渡金属螯合能力影响的计算探索:QTAIM、EDA 和 CDA 分析","authors":"Suzane Leonie Djendo Mazia, Moto Ongagna Jean, Adjieufack Abel Idrice, Daniel Lissouck, Jean Claude Ndom, Désiré Bikele Mama","doi":"10.1002/qua.27495","DOIUrl":null,"url":null,"abstract":"<div>\n \n <p>We have explored the chelation of dimethylglyoxime ligand to divalent (nd<sup><i>x</i></sup>: <i>x</i> = 6, 7, 8) transition metal (TM) cations in two media (gas phase and water) at the B3LYP//LANL2DZ/6–311+G (d,p) and B3LYP/def2-TZVP level at lower multiplicity and higher multiplicity states. Majority of the 18 optimized halide (chloride and bromide) complexes prefer square planar configuration. The correlations discerned between the experimental structural data and their estimated counterparts demonstrate a good credibility for complexes at lower multiplicity state. The basis set superposition errors (BSSEs) estimated is very small which reflects the fact that the choice of different basis sets (B3LYP//LANL2DZ/6–311+G (d,p)) introduces a slight bias in the calculation of energies. The ADMP (atom-centered density matrix propagation) simulations in water on chloride complexes indicate the irreversible nature of these M—N dissociation in trajectory simulation process. This fact explains our exclusive focus on the examination of the [glyoxime ligand]…[MX<sub>2</sub>] interactions. In addition, the solvation of (3d and 4d) transition metal chloride complexes causes a sensitive augmentation of the metal ion affinity (MIA) with an average of 0.29 and 0.24 kcal/mol. In both multiplicity states, the topological parameters have illustrated that the M—N and M—X bonds are typical metal–ligand in both media. The average Δ<i>E</i><sub>orb</sub>/Δ<i>E</i><sub>steric</sub> ratio equal to 0.45 and 0.11 in gas phase and water, respectively, reveals the predominance of the contributions from non-covalent bonding interactions (NCI) compared to those of covalent bonding. But, the maximal value equal to 6.760 is obtained for bromide rhodium complex in water. NBO analysis in both media highlights the fact that a more pronounced ionic character is observed for the majority of the chloride complexes at both spin multiplicity states because of their higher retained charges on the metal atom. For [dimethylglyoxime]…[MX<sub>2</sub>] interaction (X = Cl and Br), the charge decomposition analysis demonstrates that the lowest value of the <i>d</i>/<i>b</i> ratio is found for the chloride platinum complex at lower multiplicity state in water. This is a proof of its strong relativistic effects.</p>\n </div>","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":"124 21","pages":""},"PeriodicalIF":2.3000,"publicationDate":"2024-10-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Computational Exploration of the Impact of Low-Spin and High-Spin Ground State on the Chelating Ability of Dimethylglyoxime Ligand on Dihalo Transition Metal: A QTAIM, EDA, and CDA Analysis\",\"authors\":\"Suzane Leonie Djendo Mazia, Moto Ongagna Jean, Adjieufack Abel Idrice, Daniel Lissouck, Jean Claude Ndom, Désiré Bikele Mama\",\"doi\":\"10.1002/qua.27495\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div>\\n \\n <p>We have explored the chelation of dimethylglyoxime ligand to divalent (nd<sup><i>x</i></sup>: <i>x</i> = 6, 7, 8) transition metal (TM) cations in two media (gas phase and water) at the B3LYP//LANL2DZ/6–311+G (d,p) and B3LYP/def2-TZVP level at lower multiplicity and higher multiplicity states. Majority of the 18 optimized halide (chloride and bromide) complexes prefer square planar configuration. The correlations discerned between the experimental structural data and their estimated counterparts demonstrate a good credibility for complexes at lower multiplicity state. The basis set superposition errors (BSSEs) estimated is very small which reflects the fact that the choice of different basis sets (B3LYP//LANL2DZ/6–311+G (d,p)) introduces a slight bias in the calculation of energies. The ADMP (atom-centered density matrix propagation) simulations in water on chloride complexes indicate the irreversible nature of these M—N dissociation in trajectory simulation process. This fact explains our exclusive focus on the examination of the [glyoxime ligand]…[MX<sub>2</sub>] interactions. In addition, the solvation of (3d and 4d) transition metal chloride complexes causes a sensitive augmentation of the metal ion affinity (MIA) with an average of 0.29 and 0.24 kcal/mol. In both multiplicity states, the topological parameters have illustrated that the M—N and M—X bonds are typical metal–ligand in both media. The average Δ<i>E</i><sub>orb</sub>/Δ<i>E</i><sub>steric</sub> ratio equal to 0.45 and 0.11 in gas phase and water, respectively, reveals the predominance of the contributions from non-covalent bonding interactions (NCI) compared to those of covalent bonding. But, the maximal value equal to 6.760 is obtained for bromide rhodium complex in water. NBO analysis in both media highlights the fact that a more pronounced ionic character is observed for the majority of the chloride complexes at both spin multiplicity states because of their higher retained charges on the metal atom. For [dimethylglyoxime]…[MX<sub>2</sub>] interaction (X = Cl and Br), the charge decomposition analysis demonstrates that the lowest value of the <i>d</i>/<i>b</i> ratio is found for the chloride platinum complex at lower multiplicity state in water. 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Computational Exploration of the Impact of Low-Spin and High-Spin Ground State on the Chelating Ability of Dimethylglyoxime Ligand on Dihalo Transition Metal: A QTAIM, EDA, and CDA Analysis
We have explored the chelation of dimethylglyoxime ligand to divalent (ndx: x = 6, 7, 8) transition metal (TM) cations in two media (gas phase and water) at the B3LYP//LANL2DZ/6–311+G (d,p) and B3LYP/def2-TZVP level at lower multiplicity and higher multiplicity states. Majority of the 18 optimized halide (chloride and bromide) complexes prefer square planar configuration. The correlations discerned between the experimental structural data and their estimated counterparts demonstrate a good credibility for complexes at lower multiplicity state. The basis set superposition errors (BSSEs) estimated is very small which reflects the fact that the choice of different basis sets (B3LYP//LANL2DZ/6–311+G (d,p)) introduces a slight bias in the calculation of energies. The ADMP (atom-centered density matrix propagation) simulations in water on chloride complexes indicate the irreversible nature of these M—N dissociation in trajectory simulation process. This fact explains our exclusive focus on the examination of the [glyoxime ligand]…[MX2] interactions. In addition, the solvation of (3d and 4d) transition metal chloride complexes causes a sensitive augmentation of the metal ion affinity (MIA) with an average of 0.29 and 0.24 kcal/mol. In both multiplicity states, the topological parameters have illustrated that the M—N and M—X bonds are typical metal–ligand in both media. The average ΔEorb/ΔEsteric ratio equal to 0.45 and 0.11 in gas phase and water, respectively, reveals the predominance of the contributions from non-covalent bonding interactions (NCI) compared to those of covalent bonding. But, the maximal value equal to 6.760 is obtained for bromide rhodium complex in water. NBO analysis in both media highlights the fact that a more pronounced ionic character is observed for the majority of the chloride complexes at both spin multiplicity states because of their higher retained charges on the metal atom. For [dimethylglyoxime]…[MX2] interaction (X = Cl and Br), the charge decomposition analysis demonstrates that the lowest value of the d/b ratio is found for the chloride platinum complex at lower multiplicity state in water. This is a proof of its strong relativistic effects.
期刊介绍:
Since its first formulation quantum chemistry has provided the conceptual and terminological framework necessary to understand atoms, molecules and the condensed matter. Over the past decades synergistic advances in the methodological developments, software and hardware have transformed quantum chemistry in a truly interdisciplinary science that has expanded beyond its traditional core of molecular sciences to fields as diverse as chemistry and catalysis, biophysics, nanotechnology and material science.