Charge-shift bonding and its manifestations in chemistry

Shaik, Sason; Wu, Wei; Hiberty, Philippe C.

doi:10.1038/nchem.327

Cited by 328 publications

(422 citation statements)

References 54 publications

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“…This constitutes an additional insight into the bond pattern in these molecules, alternative to the VB-inspired charge-shift mechanism [28] of the instantaneous charge fluctuations between the central carbon atoms, invoked to explain the existence of "some" chemical bonding between the central carbons in the smallest propellane.…”

Section: Resultsmentioning

confidence: 99%

“…However, for more distant atomic partners such an accumulation of valence electrons can be absent, e.g., in the cross-ring π -interactions in benzene or between the bridgehead carbon atoms in small propellanes, for which the "charge-shift" bonding mechanism [28], involving instantaneous charge fluctuations due to a strong resonance between covalent and ionic VB structures, has been proposed.…”

Section: R F Nalewajski (B)mentioning

confidence: 99%

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Chemical bonds from through-bridge orbital communications in prototype molecular systems

Nalewajski

2010

J Math Chem

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The indirect components of chemical interactions between atomic orbitals are explored within the Orbital Communication Theory of the chemical bond. The conditional probabilities for such through-bridge probability propagation and the associated entropy/information measures of the bond covalency are examined. The illustrative example of the bridge components of the chemical bonds between bridgehead carbons in small propellanes is discussed using the hybrid-orbital model. The bridge π -bonds in benzene and butadiene from the inter-orbital communications involving the single intermediate atomic orbitals are probed within the Hückel description and selected higher-orders of orbital bridges, involving several orbital intermediaries, are investigated.

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Section: Resultsmentioning

confidence: 99%

Section: R F Nalewajski (B)mentioning

confidence: 99%

Chemical bonds from through-bridge orbital communications in prototype molecular systems

Nalewajski

2010

J Math Chem

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“…This charge shift bonding concept has helped increase our understanding of various 80 intriguing bonding and reactivity problems, including for example, the inverted bond in [1.1.1] propellane, and the rarity of ionic chemistry of silicon in condensed phase. 40,41 …”

Section: V2 Hypervalency and Charge-shift Bondingmentioning

confidence: 99%

How valence bond theory can help you understand your (bio)chemical reaction

et al. 2015

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“…A classical example is the central bond in small propellanes [2,3,19,21], for which the VB-based charge-shift mechanism [17] has been proposed as an alternative explanation of its apparent existence.…”

Section: Cg Criterion Of Bond Localizationmentioning

confidence: 99%

Bond-order and entropic probes of the chemical bonds

Nalewajski

Gurdek

2012

Struct Chem

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An overview of the recent bond-order and entropy/information measures of the chemical bond multiplicity and of its covalent/ionic composition is given. The former include the Wiberg index of the molecular orbital (MO) theory and its atomic/diatomic components, while the latter explore the communication-noise (covalency) and information-flow (ionic) descriptors of molecular information channels in the atomic-orbital (AO) resolution. The illustrative application to the two-orbital model is presented and the atomic resolution of bond contributions is presented. Alternative information distributions, including densities of the displacement in the system Shannon entropy and its entropy deficiency relative to the ''promolecule,'' are advocated as effective probes of chemical bonds. They complement the familiar density difference diagrams of electron redistributions accompanying the bond formation process. These quantities are applied to investigate the central bond in small propellanes and the contragradience criterion, based upon the non-additive Fisher information in electron distribution, is shown to efficiently locate the bonding regions in butadiene and benzene. The novel, indirect bonding mechanism through the orbital intermediaries, inferred from the orbital communication theory in the AO resolution, is probed in these two illustrative p-electron systems using the generalized Wiberg bond-orders. It is shown to give rise to a more realistic representation of the second-neighbor interactions, which have previously been diagnosed as the direct (through-space) non-bonding. In MO theory, these through-bridge bond components are due to the implicit dependencies between the (non-orthogonal) AO projections onto the molecular bonding subspace of the occupied MO. They do not require the bond-charge accumulation between the nuclei of bonded atoms and can be realized at longer distances. The effective range of such indirect interactions is probed in representative polymers. Finally, the entropy/information concepts for three dependent probability distributions are used to qualitatively examine the promotion of reactants in catalysis. The chemisorbed species are predicted to undergo an ionic promotion, compared to the gas-phase reference, thus exhibiting more deterministic communications on the catalytic surface.

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Charge-shift bonding and its manifestations in chemistry

Cited by 328 publications

References 54 publications

Chemical bonds from through-bridge orbital communications in prototype molecular systems

Chemical bonds from through-bridge orbital communications in prototype molecular systems

How valence bond theory can help you understand your (bio)chemical reaction

Bond-order and entropic probes of the chemical bonds

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