X-ray diffraction and QTAIM calculations of the non-covalent intermolecular fluorine-fluorine interactions in tris(trifluoroacetylacetonato)-manganese(III)

Gostynski, Roxanne; Rooyen, Petrus H. van; Conradie, Jeanet

doi:10.1016/j.molstruc.2019.127119

Cited by 6 publications

(3 citation statements)

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“…The AIM molecular graphs of B 2 F 6 , B 2 Cl 6 , BAlF 6 , and BAlCl 6 (second row in Figure ) evidence that the B 2 F 6 and B 2 Cl 6 are not stabilized, as expected, by B···F or by B···Cl interactions, but by dispersive interactions between halogen atoms of different monomers, characterized by a very small electron density and its Laplacian at the corresponding BCP. The characteristics found for these F···F closed shell interactions are totally similar to those reported in previous works in different chemical environments. − As usual in typical dispersion-governed systems, as for instance the methane dimer, both exhibit a continuous s isosurface associated to a region of weak interactions placed between monomers (third row in Figure ), where not only the weakly attractive interactions but also the very weakly repulsive forces are revealed in a subtle balance. The ELF pattern of both dimers is very similar (see Figure S2); the only difference is a larger F lone pair population with respect to Cl, in agreement with a softer distribution of the electron density of the latter one and in line with its more complex AIM molecular graph.…”

Section: Resultssupporting

confidence: 83%

“…The characteristics found for these F···F closed shell interactions are totally similar to those reported in previous works in different chemical environments. 51 − 53 As usual in typical dispersion-governed systems, as for instance the methane dimer, 54 both exhibit a continuous s isosurface associated to a region of weak interactions placed between monomers (third row in Figure 2 ), where not only the weakly attractive interactions but also the very weakly repulsive forces are revealed in a subtle balance. The ELF pattern of both dimers is very similar (see Figure S2 ); the only difference is a larger F lone pair population with respect to Cl, in agreement with a softer distribution of the electron density of the latter one and in line with its more complex AIM molecular graph.…”

Section: Resultsmentioning

confidence: 60%

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Dispersion, Rehybridization, and Pentacoordination: Keys to Understand Clustering of Boron and Aluminum Hydrides and Halides

et al. 2023

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The structure, stability, and bonding characteristics of dimers and trimers involving BX3 and AlX3 (X = H, F, Cl) in the gas phase, many of them explored for the first time, were investigated using different DFT (B3LYP, B3LYP/D3BJ, and M06-2X) and ab initio (MP2 and G4) methods together with different energy decomposition formalisms, namely, many-body interaction-energy and localized molecular orbital energy decomposition analysis. The electron density of the clusters investigated was analyzed with QTAIM, electron localization function, NCIPLOT, and adaptive natural density partitioning approaches. Our results for triel hydride dimers and Al2X6 (X = F, Cl) clusters are in good agreement with previous studies in the literature, but in contrast with the general accepted idea that B2F6 and B2Cl6 do not exist, we have found that they are predicted to be weakly bound systems if dispersion interactions are conveniently accounted for in the theoretical schemes used. Dispersion interactions are also dominant in both homo- and heterotrimers involving boron halide monomers. Surprisingly, B3F9 and B3Cl9 C 3v cyclic trimers, in spite of exhibiting rather strong B–X (X = F, Cl) interactions, were found to be unstable with respect to the isolated monomers due to the high energetic cost of the rehybridization of the B atom, which is larger than the two- and three-body stabilization contributions when the cyclic is formed. Another important feature is the enhanced stability of both homo- and heterotrimers in which Al is the central atom because Al is systematically pentacoordinated, whereas this is not the case when the central atom is B, which is only tri- or tetra-coordinated.

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Section: Resultssupporting

confidence: 83%

Section: Resultsmentioning

confidence: 60%

Dispersion, Rehybridization, and Pentacoordination: Keys to Understand Clustering of Boron and Aluminum Hydrides and Halides

et al. 2023

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“…The manganese(III) ion is a d 4 transition metal making it possible to exhibit the Jahn–Teller distortion. The Jahn–Teller distortion has been examined and reported in several systems. − Although the Jahn–Teller distortion has been reported in several systems, there has been no previous report of Jahn–Teller distortion in Mn 3+ (H 2 O) 6 and Mn 3+ (NH 3 ) 6 complexes. Therefore, the Jahn–Teller effects have been examined in Mn 3+ (H 2 O) 6 and Mn 3+ (NH 3 ) 6 complexes to locate the elongated and the compressed configurations.…”

Section: Introductionmentioning

confidence: 99%

Solvation of Manganese(III) Ion in Water and in Ammonia

Malloum

Conradie

2023

J. Phys. Chem. A

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In this work, we have studied the solvation of manganese(III) ion in water and in ammonia using three levels of theory: MP2, MN15, and ωB97XD associated with the aug-cc-pVDZ basis set. The studied systems are constituted of Mn3+(H2O)6 and Mn3+(NH3)6 in gas and solvent phases as well as Mn3+(H2O)18 and Mn3+(NH3)18 in the gas phase. Four aspects of the solvation of manganese(III) ion have been examined for the aforementioned systems at the three levels of theory. First, we started by locating the Jahn–Teller elongated and compressed configuration in Mn3+(H2O)6 and Mn3+(NH3)6. Second, we calculated the spin state energies and the spin state free energies for temperatures ranging from 50 to 400 K to look at possible spin crossover in the studied systems. Third, we carried out a quantum theory of atoms in molecules (QTAIM) analysis, and we determined the ionic radii of manganese(III) ion in water and in ammonia. Fourth, we calculated the solvation free energies and the solvation enthalpies of manganese(III) ion in water and in ammonia using the cluster continuum solvation model. For these four aspects of the solvation of manganese(III) ion, most of the reported properties are provided in this work for the first time. We particularly found that the calculated solvation enthalpy of the manganese(III) ion in water is in good agreement with an experimental estimate.

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Density functional theory calculated data of different electronic states and bond stretch isomers of tris(trifluoroacetylacetonato)-manganese(III)

Conradie

2019

Data in Brief

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In this data article, using density functional theory calculations, it is shown that in the gas phase, free from crystal packing effects, different elongation and compression Jahn-Teller geometries of fac and mer tris(trifluoroacetylacetonato)-manganese(III) are possible. A careful construction of input geometries made it possible to obtain the density functional theory calculated optimized geometries of different elongation and compression Jahn-Teller geometries of fac and mer tris(trifluoroacetylacetonato)-manganese(III). The mer CF3–CF3 elongation isomer has the lowest energy (Fig. 1), while in the solid state a mer CH3–CH3 compression tris(trifluoroacetylacetonato)-manganese(III) isomer is experimentally characterized [1]. The rare experimental example of a compression tris(β-diketonato)-manganese(III) structure is ascribed to intermolecular F⋯F and F⋯H interactions between the tris(trifluoroacetylacetonato)-manganese(III) molecules in the solid crystalline state, contributing to the distortion of the coordination polyhedron of tris(trifluoroacetylacetonato)-manganese(III) from the expected elongation Jahn-Teller geometry, to the observed higher energy electronic state with compression Jahn-Teller distortion.

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X-ray diffraction and QTAIM calculations of the non-covalent intermolecular fluorine-fluorine interactions in tris(trifluoroacetylacetonato)-manganese(III)

Cited by 6 publications

References 50 publications

Dispersion, Rehybridization, and Pentacoordination: Keys to Understand Clustering of Boron and Aluminum Hydrides and Halides

Dispersion, Rehybridization, and Pentacoordination: Keys to Understand Clustering of Boron and Aluminum Hydrides and Halides

Solvation of Manganese(III) Ion in Water and in Ammonia

Density functional theory calculated data of different electronic states and bond stretch isomers of tris(trifluoroacetylacetonato)-manganese(III)

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