Coordination’s preference and electronic structure of N-heterocyclic carbene–monometallic complexes: DFT evaluation of σ-bonding and π-backbonding interactions

Mokrane, Zahia; Zouchoune, Bachir; Zaiter, Abdallah

doi:10.1007/s00214-020-02628-6

Cited by 10 publications

(4 citation statements)

References 56 publications

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“…To highlight and evaluate the hydrogen bonding between DMT and β-CD in gas and aqueous phases, the Morokuma and Ziegler-Rauk energy decomposition analysis (EDA) [83-85] was applied, which was widely used previously [86][87][88][89][90][91][92][93]. Thus, the EDA using the hybrid B3LYP-D3 functional gives rise to the resulting interaction energy ΔEint which is decomposed into four terms of energy as given below: the electrostatic interaction ΔEelstat which is an attractive interaction, the Pauli interaction ΔEPauli that exhibits a repulsive interaction, the orbital interaction ΔEorb as an attractive term refers to the charge transfer between the occupied orbitals and the unoccupied orbitals of the two fragments and nally ΔEdisp corresponding to the Grimme dispersion correction term.…”

Section: Energy Decomposition Analysis (Eda)mentioning

confidence: 99%

Computational investigation of dimethoate and β-cyclodextrin inclusion complex: molecular structures, intermolecular interactions, and electronic analysis

et al. 2023

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The proposed study concerns the inclusion complexation of dimethoate (DMT) in the β-cyclodextrin (β-CD) molecule cage using a 1:1 stoichiometry. The interactions between DMT and -CD were evaluated using PM7 and DFT in water and gas with base 6-31G(d,p); using the CAMB3LYP functional.All approaches agree with the optimal 3D structure, which includes full DMT inclusion in the CD cavity. Complexation, LUMO, and HOMO energies were computed. The natural bond orbital (NBO) and UV-visible calculations were determined and discussed. Additionally, the non-covalent intermolecular interactions between dimethoate and β-cyclodextrin are investigated through: reduced density gradient (RDG), non-covalent interaction (NCI) and independent gradient model (IGM) that the main forces stabilizing the examined inclusion complex are H-bond and Van Der Waals interactions. Furthermore, the energy decomposition analysis (EDA) emphasizes the importance of the H-bond as attractive interactions.

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Section: Energy Decomposition Analysis (Eda)mentioning

confidence: 99%

Computational investigation of dimethoate and β-cyclodextrin inclusion complex: molecular structures, intermolecular interactions, and electronic analysis

et al. 2023

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Section: Energy Decomposition Analysis (Eda)mentioning

confidence: 99%

Computational investigation of dimethoate and β-Cyclodextrin inclusion complex: molecular structures, intermolecular interactions and electronic analysis

Benaissa

Bouhadiba

Naili

et al. 2022

Preprint

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The proposed study concerns the inclusion complexation of dimethoate (DMT) in the β-cyclodextrin (β-CD) molecule cage using a 1:1 stoichiometry. The interactions between DMT and -CD were evaluated using PM7 and DFT in water and gas with base 6-31G(d,p); using the CAMB3LYP functional. All approaches agree with the optimal 3D structure, which includes full DMT inclusion in the CD cavity. Complexation, LUMO, and HOMO energies were computed. The natural bond orbital (NBO) and UV- visible calculations were determined and discussed. Additionally, the non-covalent intermolecular interactions between dimethoate and β-cyclodextrin are investigated through: reduced density gradient (RDG), non-covalent interaction (NCI) and independent gradient model (IGM) that the main forces stabilizing the examined inclusion complex are H-bond and Van Der Waals interactions. Furthermore, the energy decomposition analysis (EDA) emphasizes the importance of the H-bond as attractive interactions.

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“…In order to explore and to understand the electronic structure, bonding properties, and chemical stability of the aforementioned binuclear complexes (Scheme 1), we provide a complete rationalization of their bonding by means of a theoretical DFT analysis using the generalized gradient approximation (BP86) and the hybrid B3LYP* levels and supported by the energy decomposition analysis (EDA) [50–52] exploiting the σ‐donation (L → M) and π‐backdonation (L ← M) capabilities of the interacting ligands [53, 54]. These functionals have been proved to reproduce the available experimental data and investigate the electronic properties of related mono‐ and dinuclear transition metal complexes [29, 55–69].…”

Section: Introductionmentioning

confidence: 99%

“…M) and π-backdonation (L M) capabilities of the interacting ligands [53,54]. These functionals have been proved to reproduce the available experimental data and investigate the electronic properties of related mono-and dinuclear transition metal complexes [29,[55][56][57][58][59][60][61][62][63][64][65][66][67][68][69].…”

mentioning

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Terminal and bridging ligand effects on M(I)M(I) multiple bonding: ADFTinvestigation of the coordination in (X)[M₂Cl]L₂complexes (M = Cr,Fe,L = CO,PEt₃,X = Cl, allyl,Cp, and indenyl)

Mecheri

Zouchoune

2023

Int J of Quantum Chemistry

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A theoretical DFT investigation has been achieved on (X)[M2Cl]L2 (M = Cr, Fe, L = CO, PEt3, and X = allyl, cyclopentadienyl, and indenyl) complexes by means of BP86 and B3LYP* functionals. The geometry optimizations showed an η3‐coordination for the allyl, while Cp and indenyl ligands adopt the same η5‐coordination mode and the chloride acts as bridging ligand. The metal–metal bond distances are very sensitive to the replacement of the CO with PEt3 (triethylphosphine) with regard to the electron‐donation and electron π‐backdonation properties for the former and only to the electron‐donation for the later. This replacement impacts drastically the metal–metal bonding. Changing the metal from Cr to Fe increases the metal–metal bond distance, decreases the bond order and the oxidation sate of Fe, in agreement with the decrease of Wiberg bond indices (WBI) and Mayer bond order values (MBO). The findings showed that the Cl− and allyl− behave as 4‐electron donors, while Cp− and Ind− behave as 6–electron donors leading to outstanding electron properties stemming from different coordination, which are clarified by the σ‐donation and π‐backdonation properties, which are highlighted by the orbitals' populations and the energy decomposition analysis (EDA). Based on the aforementioned information, the chromium and iron complexes of Cl− and allyl− are of 22‐ and 24‐metal valence electrons (MVE), where those of Cp− and Ind− are of 26‐ and 28‐MVE, respectively. It is well noted that the metal–metal multiple bonding overcomes the electrons' deficiency.

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Coordination’s preference and electronic structure of N-heterocyclic carbene–monometallic complexes: DFT evaluation of σ-bonding and π-backbonding interactions

Cited by 10 publications

References 56 publications

Computational investigation of dimethoate and β-cyclodextrin inclusion complex: molecular structures, intermolecular interactions, and electronic analysis

Computational investigation of dimethoate and β-cyclodextrin inclusion complex: molecular structures, intermolecular interactions, and electronic analysis

Computational investigation of dimethoate and β-Cyclodextrin inclusion complex: molecular structures, intermolecular interactions and electronic analysis

Terminal and bridging ligand effects on M(I)M(I) multiple bonding: ADFTinvestigation of the coordination in (X)[M₂Cl]L₂complexes (M = Cr,Fe,L = CO,PEt₃,X = Cl, allyl,Cp, and indenyl)

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Coordination’s preference and electronic structure of N-heterocyclic carbene–monometallic complexes: DFT evaluation of σ-bonding and π-backbonding interactions

Cited by 10 publications

References 56 publications

Computational investigation of dimethoate and β-cyclodextrin inclusion complex: molecular structures, intermolecular interactions, and electronic analysis

Computational investigation of dimethoate and β-cyclodextrin inclusion complex: molecular structures, intermolecular interactions, and electronic analysis

Computational investigation of dimethoate and β-Cyclodextrin inclusion complex: molecular structures, intermolecular interactions and electronic analysis

Terminal and bridging ligand effects on M(I)M(I) multiple bonding: ADFTinvestigation of the coordination in (X)[M2Cl]L2complexes (M = Cr,Fe,L = CO,PEt3,X = Cl, allyl,Cp, and indenyl)

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Terminal and bridging ligand effects on M(I)M(I) multiple bonding: ADFTinvestigation of the coordination in (X)[M₂Cl]L₂complexes (M = Cr,Fe,L = CO,PEt₃,X = Cl, allyl,Cp, and indenyl)