Bond orders and electron delocalization indices for S–N, S–C and S–S bonds in 1,2,3-dithiazole systems

Барташевич, Е. В.; Mukhitdinova, Svetlana E.; Tsirelson, Vladimir G.

doi:10.1016/j.mencom.2021.09.029

Cited by 5 publications

(5 citation statements)

References 43 publications

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“…One of such descriptors is the electron delocalization index

δ_{AB}

(DI), 45,50 which estimates the average number of the electron pairs shared between two atoms in a molecule. It is expressed via an exchange‐only component of the pair density averaged over the Baders's zero‐flux QTAIM atomic basins, 62

Ω_{i}

δ_{AB} goodbreak= goodbreak- 2 \int_{{normalΩ}_{A}} d bold-italicr \int_{{normalΩ}_{B}} d bold-italicr' ρ ((), r) h_{x} ((), bold-italicr bold, bold-italicr') .

The DI is a convenient numerical measure of the bond order and an indicator of the bond type 55,63–65 . It also facilitates revealing the correspondence between the Lewis molecular structure and the actual electron density distribution, which carries information about the electron delocalization in the molecule 44 …”

Section: Methodsmentioning

confidence: 99%

“…The DI is a convenient numerical measure of the bond order and an indicator of the bond type. 55,[63][64][65] It also facilitates revealing the correspondence between the Lewis molecular structure and the actual electron density distribution, which carries information about the electron delocalization in the molecule. 44 Another group of new quantum-chemical descriptors deals with electron (de)localization from the perspective of the exchange contribution to the electronic energy of a molecule.…”

Section: Theoretical Backgroundmentioning

confidence: 99%

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Keto‐enol tautomerism from the electron delocalization perspective

et al. 2022

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The equilibrium between keto and enol forms in acetylacetone and its derivatives is studied using electron delocalization indices and delocalization tensor density. We demonstrate how electron delocalization governs the equilibrium between keto and enol forms. The less stable enols have more distinct double and single bond character in the C C C fragment, while electron delocalization in this fragment is more pronounced in more stable enols. Looking for the origin of such behavior, we considered the one-electron potentials entering the Euler equation for the electron density. We found that electron delocalization is mainly governed by the static exchange potential, which depends on the three-dimensional atomic structure. It, however, does not distinguish differences in electron delocalization in more and less stable enols, the effect arising from the kinetic exchange contribution, which reflects spin-dependent effects in the electron motion. The local depletion of kinetic exchange in the conjugated fragment yields the enhanced electron delocalization along the C C C bonds in more stable enols. Thus, a combination of considered descriptors allowed us to reveal the influence of electron delocalization on the equilibrium between keto and enol forms and showed the significant features of this phenomenon.

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“…One of such descriptors is the electron delocalization index

δ_{AB}

Ω_{i}

δ_{AB} goodbreak= goodbreak- 2 \int_{{normalΩ}_{A}} d bold-italicr \int_{{normalΩ}_{B}} d bold-italicr' ρ ((), r) h_{x} ((), bold-italicr bold, bold-italicr') .

Section: Methodsmentioning

confidence: 99%

Section: Theoretical Backgroundmentioning

confidence: 99%

Keto‐enol tautomerism from the electron delocalization perspective

et al. 2022

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“…Further support to the donor-acceptor spodium bond nature of the Hg(II)•••Pd(II) interaction is provided in Figure 4, where it is represented the electron density (ED) and electrostatic potential (ESP) functions along the path connecting the Hg and Pd atoms. It has been demonstrated [19 that the relative arrangement of ED and ESP minima positions provides unambiguous information regarding the type of donor-acceptor noncovalent interaction. That is, the minimum of ESP along the bond path is located closer to the atom that donates electrons, whereas the minimum of ED is located closer to the atom that acts as the electrophilic site.…”

Section: Resultsmentioning

confidence: 99%

Hg(II)⋅d⁸[M] Interactions: Are they Metallophilic Interactions or Spodium Bonds?

Burguera,

Bauzá,

Frontera

2023

ChemPhysChem

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Some literature reports have shown the existence of short Hg(II)···d8[M] (M = Pd, Pt) contacts between linear Hg(II) and square planar d8[M] complexes that have been defined as heterometallophilic interactions. Linear L–Hg(II)–L complexes exhibit a π‐hole or positive belt of electrostatic potential at the Hg atom, while late transition metals can serve as effective electron donors through their filled dz2 orbitals. This study provides compelling evidence that Hg(II)···d8[M] interactions should be more appropriately termed Spodium bonds.

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“…The delocalization index, δ(A-B), is one of the best tools to estimate the number of delocalized electron pairs between two atoms 42,43 . Therefore, as listed in Table . 2, we calculated these indices as a tool to analyze a multicenter bonding in this cluster from one side and to describe different M…M interaction modes from another side 35 .…”

Section: M-cp Interactions In Clustermentioning

confidence: 99%

Study the Chemical Bonding of Heterometallic Trinuclear Cluster Containing Cobalt and Ruthenium: [(Cp*Co) (CpRu)2 (μ3-H) (μ-H)3] using QTAIM Approach

Hassan

Al-Ibadi

2023

Baghdad Sci.J

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The topological parameters of the metal-metal and metal-ligand bonding interactions in a trinuclear tetrahydrido cluster [(Cp*Co) (CpRu)2 (μ3-H) (μ-H)3]1 (Cp* = η5 -C5Me4Et), (Cp = η5 -C5Me5), was explored by using the Quantum Theory of Atoms-in-Molecules (QTAIM). The properties of bond critical points such as the bond delocalization indices δ (A, B), the electron density ρ(r), the local kinetic energy density G(r), the Laplacian of the electron density ∇2ρ(r), the local energy density H(r), the local potential energy density V(r) and ellipticity ε(r) are compared with data from earlier organometallic system studies. A comparison of the topological processes of different atom-atom interactions has become possible thanks to these results. In the core of the heterometallic tetrahydrido cluster, the Ru2CoH4 part, the calculations show no existence of any bond critical points (BCP) or identical bond paths (BPs) between Ru-Ru and Ru-Co. Electron densities are determined by the position of bridging hydride atoms coordinated to Ru-Ru and Ru-Co, which significantly affects the bonds between these transition metal atoms. On the other hand, the results confirm that the cluster under study contains a 7c–11e bonding interaction delocalized over M3H4, as shown by the non-negligible delocalization index calculations. The small values for electron density ρ(b) above zero, together with the small values, again above zero, for Laplacian ∇2ρ(b) and the small positive values for total energy density H(b), are shown by the Ru-H and Co-H bonds in this cluster is typical for open-shell interactions. Also, the topological data for the bond interactions between Co and Ru metal atoms with the C atoms of the cyclopentadienyl Cp ring ligands are similar. They show properties very identical to open-shell interactions in the QTAIM classification.

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Bond orders and electron delocalization indices for S–N, S–C and S–S bonds in 1,2,3-dithiazole systems

Cited by 5 publications

References 43 publications

Keto‐enol tautomerism from the electron delocalization perspective

Keto‐enol tautomerism from the electron delocalization perspective

Hg(II)⋅d⁸[M] Interactions: Are they Metallophilic Interactions or Spodium Bonds?

Study the Chemical Bonding of Heterometallic Trinuclear Cluster Containing Cobalt and Ruthenium: [(Cp*Co) (CpRu)2 (μ3-H) (μ-H)3] using QTAIM Approach

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Bond orders and electron delocalization indices for S–N, S–C and S–S bonds in 1,2,3-dithiazole systems

Cited by 5 publications

References 43 publications

Keto‐enol tautomerism from the electron delocalization perspective

Keto‐enol tautomerism from the electron delocalization perspective

Hg(II)⋅d8[M] Interactions: Are they Metallophilic Interactions or Spodium Bonds?

Study the Chemical Bonding of Heterometallic Trinuclear Cluster Containing Cobalt and Ruthenium: [(Cp*Co) (CpRu)2 (μ3-H) (μ-H)3] using QTAIM Approach

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Product

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Hg(II)⋅d⁸[M] Interactions: Are they Metallophilic Interactions or Spodium Bonds?