A Valence Bond Study of Three-Center Four-Electron π Bonding: Electronegativity vs Electroneutrality

DeBlase, Andrew F.; Licata, Megan; Galbraith, John Morrison

doi:10.1021/jp800010h

Cited by 19 publications

(10 citation statements)

References 44 publications

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“…These factors appear lucidly in the VB projection of the MO model, as originally proposed by Coulson . Indeed, using VB theory, some of the present authors have recently shown that the stable 3c/4e bonds are CSBs. This is demonstrated below.…”

Section: Charge‐shift Bonding In Hypervalent (Three‐center Four‐electron) Systemsmentioning

confidence: 99%

Charge‐Shift Bonding: A New and Unique Form of Bonding

et al. 2019

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Stichwçrter: bond theory ·charge-shift bonds · covalent bonds ·ionic bonds ·v alence bonds Dedicated to Roald HoffmannAbstract: Charge-shift bonds (CSBs) constitute anew class of bonds different than covalent/polar-covalent and ionic bonds. Bonding in CSBs does not arise from either the covalent or the ionic structures of the bond, but rather from the resonance interaction between the structures.T his Essay describes the reasons why the CSB family was overlooked by valence-bond pioneers and then demonstrates that the unique status of CSBs is not theory-dependent. Thus,v alence bond (VB), molecular orbital (MO), and energy decomposition analysis (EDA), as well as av ariety of electron density theories all show the distinction of CSBs vis-à-vis covalent and ionic bonds. Furthermore,t he covalent-ionic resonance energy can be quantified from experiment, and hence has the same essential status as resonance energies of organic molecules,e .g., benzene. The Essaye nds by arguing that CSBs are ad istinct family of bonding,w ith ap otential to bring about aR enaissance in the mental map of the chemical bond, and to contribute to productive chemical diversity.

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Section: Charge‐shift Bonding In Hypervalent (Three‐center Four‐electron) Systemsmentioning

confidence: 99%

Charge‐Shift Bonding: A New and Unique Form of Bonding

et al. 2019

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“…Ozone has considerable (∼33%) singlet diradical character 25, 26. For the d 9 Cu(II) complex cations, the unpaired electron lies in the plane of the ligands and hence is inaccessible to ozone; therefore, the Cu(II) cations are unreactive toward ozone.…”

Section: Resultsmentioning

confidence: 99%

Production and isolation of ligated metal(IV)‐oxo ions by tandem mass spectrometry

Taylor¹,

Blanksby²,

Colbran³

et al. 2010

Rapid Comm Mass Spectrometry

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High valent metal(IV)-oxo species, [M(==O)(MeIm)(n)(OAc)](+) (M = Mn-Ni, MeIm = 1-methylimidazole, n = 1-2), which are relevant to biology and oxidative catalysis, were produced and isolated in gas-phase reactions of the metal(II) precursor ions [M(MeIm)(n)(OAc)](+) (M = Mn-Zn, n = 1-3) with ozone. The precursor ions [M(MeIm)(OAc)](+) and [M(MeIm)(2)(OAc)](+) were generated via collision-induced dissociation of the corresponding [M(MeIm)(3)(OAc)](+) ion. The dependence of ozone reactivity on metal and coordination number is discussed.

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“…The dramatic differences in the physical and chemical properties of O 3 and SO 2 indicate that the electronic structures of these two species are significantly different despite the fact that they are isovalent molecules. A number of theoretical and computational studies of O 3 and SO 2 have been undertaken to understand the differences in the electronic structure of these species. − The general consensus, with few exceptions, has been that the differences between O 3 and SO 2 are a result of a significant measure of diradical character in O 3 in contrast to the closed-shell nature of SO 2 .…”

Section: Review and Discussionmentioning

confidence: 99%

Insights into the Electronic Structure of Molecules from Generalized Valence Bond Theory

Dunning

Takeshita

et al. 2016

J. Phys. Chem. A

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In this article we describe the unique insights into the electronic structure of molecules provided by generalized valence bond (GVB) theory. We consider selected prototypical hydrocarbons as well as a number of hypervalent molecules and a set of first- and second-row valence isoelectronic species. The GVB wave function is obtained by variationally optimizing the orbitals and spin coupling in the valence bond wave function. The GVB wave function is a generalization of the Hartree–Fock (HF) wave function, lifting the double occupancy restriction on a subset of the HF orbitals as well as the associated orthogonality and spin coupling constraints. The GVB wave function includes a major fraction (if not all) of the nondynamical correlation energy of a molecule. Because of this, GVB theory properly describes bond formation and can answer one of the most compelling questions in chemistry: How are atoms changed by molecular formation? We show that GVB theory provides a unified description of the nature of the bonding in all of the above molecular species as well as contributing new insights into the well-known, but poorly understood, first-row anomaly.

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A Valence Bond Study of Three-Center Four-Electron π Bonding: Electronegativity vs Electroneutrality

Cited by 19 publications

References 44 publications

Charge‐Shift Bonding: A New and Unique Form of Bonding

Charge‐Shift Bonding: A New and Unique Form of Bonding

Production and isolation of ligated metal(IV)‐oxo ions by tandem mass spectrometry

Insights into the Electronic Structure of Molecules from Generalized Valence Bond Theory

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