The structure of IF3

Hoyer, Sevim; Seppelt, Konrad

doi:10.1002/(sici)1521-3773(20000417)39:8<1448::aid-anie1448>3.0.co;2-g

Cited by 28 publications

(31 citation statements)

References 12 publications

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“…Each stationary point was confirmed as a minimum by absence of imaginary normal mode frequencies. Available experimental geometries for the ICl 3 dimer, IF 3 , IF 5 , dichloroiodobenzene (PhICl 2 ), and diacetoxyiodobenzene (PhI(OAc) 2 ) [18,[63][64][65][66] were used to gauge the accuracy of the DFT calculations. Experimental and calculated geometries using different model chemistries for this set of compounds are compared in Tables A1 and A2 (See Appendix A).…”

Section: Methodsmentioning

confidence: 99%

A Continuum from Halogen Bonds to Covalent Bonds: Where Do λ3 Iodanes Fit?

et al. 2019

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The intrinsic bonding nature of λ 3 -iodanes was investigated to determine where its hypervalent bonds fit along the spectrum between halogen bonding and covalent bonding. Density functional theory with an augmented Dunning valence triple zeta basis set ( ω B97X-D/aug-cc-pVTZ) coupled with vibrational spectroscopy was utilized to study a diverse set of 34 hypervalent iodine compounds. This level of theory was rationalized by comparing computational and experimental data for a small set of closely-related and well-studied iodine molecules and by a comparison with CCSD(T)/aug-cc-pVTZ results for a subset of the investigated iodine compounds. Axial bonds in λ 3 -iodanes fit between the three-center four-electron bond, as observed for the trihalide species IF 2 − and the covalent FI molecule. The equatorial bonds in λ 3 -iodanes are of a covalent nature. We explored how the equatorial ligand and axial substituents affect the chemical properties of λ 3 -iodanes by analyzing natural bond orbital charges, local vibrational modes, the covalent/electrostatic character, and the three-center four-electron bonding character. In summary, our results show for the first time that there is a smooth transition between halogen bonding → 3c–4e bonding in trihalides → 3c–4e bonding in hypervalent iodine compounds → covalent bonding, opening a manifold of new avenues for the design of hypervalent iodine compounds with specific properties.

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Section: Methodsmentioning

confidence: 99%

A Continuum from Halogen Bonds to Covalent Bonds: Where Do λ3 Iodanes Fit?

et al. 2019

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“…Most of the X-Y bond in interhalogens is much weaker than the X-X bond in halogens, except for the F-F bond because F has the strongest electronegativity with the possible ionic charge of only −1. The IF is a powder below −58°C and sublimates at −14°C which cannot be isolated as a pure substance and should disproportionate rapidly into elemental iodine and iodine trifluoride at room temperature 21 .…”

Section: Results and Discussion Synthesis And Characterization Of 2d mentioning

confidence: 99%

Two-dimensional iodine-monofluoride epitaxy on WSe2

et al. 2021

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Interhalogen compounds (IHCs) are extremely reactive molecules used for halogenation, catalyst, selective etchant, and surface modification. Most of the IHCs are unstable at room temperature especially for the iodine-monofluoride (IF) whose structure is still unknown. Here we demonstrate an unambiguous observation of two-dimensional (2D) IF bilayer grown on the surface of WSe2 by using scanning transmission electron microscopy and electron energy loss spectroscopy. The bilayer IF shows a clear hexagonal lattice and robust epitaxial relationship with the WSe2 substrate. Despite the IF is known to sublimate at −14 °C and has never found as a solid form in the ambient condition, but surprisingly it is found stabilized on a suitable substrate and the stabilized structure is supported by a density functional theory. This 2D form of IHC is actually a byproduct during a chemical vapor deposition growth of WSe2 in the presence of alkali metal halides as a growth promoter and requires immediate surface passivation to sustain. This work points out a great possibility to produce 2D structures that are unexpected to be crystallized or cannot be obtained by a simple exfoliation but can be grown only on a certain substrate.

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“…It has long been known that hypervalent XF 3 (X = Cl, Br, I) molecules of group‐17 elements adopt T‐shaped C 2V geometries (see Fig. ), as evidenced by gas phase experiments for ClF 3 and

{BrF}_{3,}^{[}

] and condensed phase experiments for IF 3 . Moreover, a structure of the same type is predicted by numerous quantum mechanical calculations for the AtF 3 analogue, even if this has not yet been experimentally confirmed.…”

Section: Introductionmentioning

confidence: 99%

“…1), as evidenced by gas phase experiments for ClF 3 and BrF ½ 3; [1][2][3]] and condensed phase experiments for IF 3 . [4] Moreover, a structure of the same type is predicted by numerous quantum mechanical calculations for the AtF 3 analogue, [5][6][7] even if this has not yet been experimentally confirmed. In contrast to chlorine, bromine or iodine fluorides, the attempts to form astatine fluorides turned out to be unsuccessful.…”

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confidence: 96%

The bonding picture in hypervalent XF₃ (X = Cl, Br, I, At) fluorides revisited with quantum chemical topology

et al. 2017

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Hypervalent XF (X = Cl, Br, I, At) fluorides exhibit T-shaped C equilibrium structures with the heavier of them, AtF , also revealing an almost isoenergetic planar D structure. Factors explaining this behavior based on simple "chemical intuition" are currently missing. In this work, we combine non-relativistic (ClF ), scalar-relativistic and two-component (X = Br - At) density functional theory calculations, and bonding analyses based on the electron localization function and the quantum theory of atoms in molecules. Typical signatures of charge-shift bonding have been identified at the bent T-shaped structures of ClF and BrF , while the bonds of the other structures exhibit a dominant ionic character. With the aim of explaining the D structure of AtF , we extend the multipole expansion analysis to the framework of two-component single-reference calculations. This methodological advance enables us to rationalize the relative stability of the T-shaped C and the planar D structures: the Coulomb repulsions between the two lone-pairs of the central atom and between each lone-pair and each fluorine ligand are found significantly larger at the D structures than at the C ones for X = Cl - I, but not with X = At. This comes with the increasing stabilization, along the XF series, of the planar D structure with respect to the global T-shaped C minima. Hence, we show that the careful use of principles that are at the heart of the valence shell electron pair repulsion model provides reasonable justifications for stable planar D structures in AX E systems. © 2017 Wiley Periodicals, Inc.

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The structure of IF3

Cited by 28 publications

References 12 publications

A Continuum from Halogen Bonds to Covalent Bonds: Where Do λ3 Iodanes Fit?

A Continuum from Halogen Bonds to Covalent Bonds: Where Do λ3 Iodanes Fit?

Two-dimensional iodine-monofluoride epitaxy on WSe2

The bonding picture in hypervalent XF₃ (X = Cl, Br, I, At) fluorides revisited with quantum chemical topology

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The structure of IF3

Cited by 28 publications

References 12 publications

A Continuum from Halogen Bonds to Covalent Bonds: Where Do λ3 Iodanes Fit?

A Continuum from Halogen Bonds to Covalent Bonds: Where Do λ3 Iodanes Fit?

Two-dimensional iodine-monofluoride epitaxy on WSe2

The bonding picture in hypervalent XF3 (X = Cl, Br, I, At) fluorides revisited with quantum chemical topology

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The bonding picture in hypervalent XF₃ (X = Cl, Br, I, At) fluorides revisited with quantum chemical topology