Chemical Bonding in Molecules and Complexes Containing d-Elements Based on DFT

Atanasov, Mihail; Daul, Claude; Fowe, Emmanuel Penka

doi:10.1007/s00706-005-0310-2

Cited by 12 publications

(4 citation statements)

References 39 publications

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“…The ELF values fall in the range between 0 and 1. ELF = 0 represents no localization of electron, while ELF = 1 shows a completely localized situation, , which can give valuable information on chemical bonds. − The ELF values (about 0.36–0.41) of U–M bonds for the L Ar U–MCp(CO) 2 complexes indicate that the U–M bonds possess modest covalent character, which is consistent with the analysis of QTAIM.…”

Section: U–m Bonding Naturesupporting

confidence: 80%

Theoretical Study on Unsupported Uranium–Metal Bonding in Uranium–Group 8 Complexes

Chi

Hao

et al. 2018

Organometallics

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On the basis of the first structurally authenticated L Ar U− FeCp(CO) 2 (L Ar = deprotonated p-terphenyl bis(aniline) ligand) complex bearing an unsupported U−Fe bond, we expanded the structures of complexes L Ar U−MCp(CO) 2 (M = Fe, Ru, Os) and systematically investigated the U−M bonding nature by using scalar-relativistic quantum chemical calculations. Theoretical results reveal highly polarized U−M interactions in the three L Ar U−MCp(CO) 2 complexes. Moreover, the three U−M bonds are confirmed to show single bond feature. Topology of electron density reveals predominantly "closed shell" U−M interaction with obvious ionic interaction in the three L Ar U−MCp(CO) 2 complexes. In addition, the negative binding energy suggests that the three L Ar U− MCp(CO) 2 complexes are thermodynamically feasible. This work reveals the bonding nature of the three U−M bonds and expands our knowledge of the unsupported uranium−metal bonding in the heterobimetallic complexes.

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Section: U–m Bonding Naturesupporting

confidence: 80%

Theoretical Study on Unsupported Uranium–Metal Bonding in Uranium–Group 8 Complexes

Chi

Hao

et al. 2018

Organometallics

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“…We also analyze the bonding in our uranyl complexes using Mayer's population-based bond orders (see ref and references herein). Previous experience shows that, despite their basis-set dependence, population bond orders are a useful tool in the coordination chemistry of d-elements. , Recently, it has been shown that these population-based bond orders provide reasonable results for actinide compounds. , …”

Section: Resultsmentioning

confidence: 99%

Relativistic Density Functional Theory Study of Dioxoactinide(VI) and -(V) Complexation with Alaskaphyrin and Related Schiff-Base Macrocyclic Ligands

2006

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Formation of complexes of alaskaphyrin 1, bi-pyen 2 and bi-tpmd 3 ligands with actinyl ions AnO2(n+), An = U, Np, Pu and n = 1, 2, was studied using density functional theory (DFT) within the scalar relativistic four-component approximation. The alaskaphyrin complexes of the uranyl are predicted to have a bent conformation, in contrast to the experimentally available X-ray data. This deviation is likely due to crystal packing effects. Apart from these conformational differences, calculated geometry parameters and vibrational frequencies are in agreement with the available experimental data. The character of bonding in the complexes is investigated using bond order analysis and extended transition states (ETS) energy decomposition. Metal-to-ligand bonds can be described as primarily ionic although substantial charge transfer is observed as well. Based on ETS analysis, it is shown that steric and/or fit/misfit requirements of actinyl cations to the ligand cavities, among the studied complexes, are the most favorable for the bi-pyen ligand 2, because its flexibility allows for optimal metal-to-donor-atom distances. Planarity of the equatorial coordination sphere of the actinide atom is found to be less important than the ability of a ligand to provide optimal uranium-to-nitrogen bond lengths. Experimental differences in demetalation rates between similar alaskaphyrin, bi-pyen and bi-tpmd uranyl complexes are explained as a result of easier protonation of the Schiff-base nitrogen of the latter. Reduction potentials calculated for the uranium complexes show a good agreement with the experiment, both in relative and in absolute terms.

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“…[20] To achieve a quantitative interpretation of the interaction nature governing the fullerene encapsulation, we obtained the interaction energy ΔE int between the host (L) and guest (fullerene), which have been well-used to evaluate prototypical supramolecular interaction patterns. [48,49] The EDA [21,50,51] describes ΔE int in terms of different meaningful quantities accounting for the electrostatic interaction (ΔE elstat ) between the defined fragments and the repulsive exchange (ΔE Pauli ) interaction because of the four-electron/two-orbital repulsion between occupied orbitals from the different fragments. The orbital (covalent) interaction (ΔE orb ) comes from the orbital relaxation and the orbital mixing between the fragments.…”

Section: Computational Detailsmentioning

confidence: 99%

Nature of C₆₀ and C₇₀ fullerene encapsulation in a porphyrin‐ and metalloporphyrin‐based cage: Insights from dispersion‐corrected density functional theory calculations

González

Mondal

Ocayo

et al. 2019

Int J of Quantum Chemistry

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The search for efficient synthetic hosts able to encapsulate fullerenes has attracted attention with regard to the purification and formation of ordered supramolecular architectures. This study of a porphyrin-based cage as an extension of the well-described ExCage 6+ and BlueCage 6+ , involving viologen as sidearms, provides an interesting scenario where the oblate C 70 fullerene is preferred in comparison to the spherical C 60. Our results expose the nature of the fullerene-cage interaction involving $50% of dispersion-type interactions evidencing the strong πÁ Á Áπ surface stacking, with a complementary contribution by the electrostatic and orbital polarization character produced by a charge reorganization with a charge accumulation facing the porphyrin macrocycles and a charge depletion along the equator formed by the viologens sidearms. Interestingly, the central N 4 H 2 ring from each porphyrin contributes to the dispersion term via N-HÁ Á Áπ interactions, which is decreased when the metallate N 4 Zn is evaluated. Thus, the formation of stable and selective fullerene encapsulation can be achieved by taking into account two main driving forces, namely, (a) the extension of the πÁ Á Áπ and X-HÁ Á Áπ stacking surface and (b) charge reorganization over the fullerene surfaces, which can be used to control fine tuning of the encapsulation thanks to the introduction of more electron-deficient and electron-rich groups within the host cage. K E Y W O R D S fullerenes, host-guest, non-covalent interactions, porphyrin 1 | INTRODUCTION Fullerenes and their derivatives have attracted extensive attention since buckminsterfullerene (C 60) characterization [1-4] owing to their unique physicochemical properties, which are useful in a wide range of applications in material science. [5-7] Despite their relevant role, improved isolation and purification approaches are still required to achieve large-scale quantities. In this sense, selective encapsulation of fullerenes offers a key strategy in their purification after obtention methods, given by hydrocarbon combustion [8] and sublimation of carbon soot [9] among others. [10] It has been shown that the efficient and selective recognition of fullerenes can be achieved via host-guest pair formation owing to intermolecular interactions. [11,12] Currently, different molecular receptors have been used, involving bowl-like species [13-15] and cages, [16,17] where the nature of the host-guest formation is of particular importance for efficient fullerene encapsulation.

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Chemical Bonding in Molecules and Complexes Containing d-Elements Based on DFT

Cited by 12 publications

References 39 publications

Theoretical Study on Unsupported Uranium–Metal Bonding in Uranium–Group 8 Complexes

Theoretical Study on Unsupported Uranium–Metal Bonding in Uranium–Group 8 Complexes

Relativistic Density Functional Theory Study of Dioxoactinide(VI) and -(V) Complexation with Alaskaphyrin and Related Schiff-Base Macrocyclic Ligands

Nature of C₆₀ and C₇₀ fullerene encapsulation in a porphyrin‐ and metalloporphyrin‐based cage: Insights from dispersion‐corrected density functional theory calculations

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Chemical Bonding in Molecules and Complexes Containing d-Elements Based on DFT

Cited by 12 publications

References 39 publications

Theoretical Study on Unsupported Uranium–Metal Bonding in Uranium–Group 8 Complexes

Theoretical Study on Unsupported Uranium–Metal Bonding in Uranium–Group 8 Complexes

Relativistic Density Functional Theory Study of Dioxoactinide(VI) and -(V) Complexation with Alaskaphyrin and Related Schiff-Base Macrocyclic Ligands

Nature of C60 and C70 fullerene encapsulation in a porphyrin‐ and metalloporphyrin‐based cage: Insights from dispersion‐corrected density functional theory calculations

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Nature of C₆₀ and C₇₀ fullerene encapsulation in a porphyrin‐ and metalloporphyrin‐based cage: Insights from dispersion‐corrected density functional theory calculations