Central bond in the three CN.cntdot.dimers NC-CN, CN-CN and CN-NC: electron pair bonding and Pauli repulsion effects

Bickelhaupt, F. Matthias; Nibbering, N. M. M.; Wezenbeek, Egbert van; Baerends, E. J.

doi:10.1021/j100191a027

Cited by 196 publications

(121 citation statements)

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“…The orbital interaction ΔE orb accounts for charge transfer and polarization effects. 91 The ΔE orb term can be decomposed into contributions from each irreducible representation of the point group of the interacting system. This makes it possible to estimate the intrinsic strength of orbital interactions from orbitals having a' (σ) and a'' (π) symmetry quantitatively.…”

Section: Computational Sectionmentioning

confidence: 99%

Pyridine-Derived N-Heterocyclic Carbenes: An Experimental and Theoretical Evaluation of the Bonding in and Reactivity of Selected Normal and Abnormal Complexes of Nickel(II) and Palladium(II)

et al. 2010

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Section: Computational Sectionmentioning

confidence: 99%

Pyridine-Derived N-Heterocyclic Carbenes: An Experimental and Theoretical Evaluation of the Bonding in and Reactivity of Selected Normal and Abnormal Complexes of Nickel(II) and Palladium(II)

et al. 2010

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“…We use an extension to open-shell systems where an electron-pair bond is formed. [20] We stress that this energy decomposition, apart from being well established and widely practiced, is also general in the sense that the terms are defined also for high-quality (fully correlated) fragment and total wavefunctions. The definition of Pauli repulsion (or exchange repulsion) used here is generally used, for example, in the theory of intermolecular forces.…”

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confidence: 99%

The Case for Steric Repulsion Causing the Staggered Conformation of Ethane

2003

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“…It comprises the destabilizing interactions between electrons of the same spin on either fragment. The orbital interaction ∆E orb accounts for charge transfer and polarization effects [115]. In the case when the Grimme dispersion corrections [95,96] are computed, the term ∆E disp is added to Equation (2).…”

Section: Computational Detailsmentioning

confidence: 99%

Understanding the Heteroatom Effect on the Ullmann Copper-Catalyzed Cross-Coupling of X-Arylation (X = NH, O, S) Mechanism

et al. 2017

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Density Functional Theory (DFT) calculations have been carried out in order to unravel the governing reaction mechanism in copper-catalyzed cross-coupling Ullmann type reactions between iodobenzene (1, PhI) and aniline (2-NH, PhNH 2 ), phenol (2-O, PhOH) and thiophenol (2-S, PhSH) with phenanthroline (phen) as the ancillary ligand. Four different pathways for the mechanism were considered namely Oxidative Addition-Reductive Elimination (OA-RE), σ-bond Metathesis (MET), Single Electron Transfer (SET), and Halogen Atom Transfer (HAT). Our results suggest that the OA-RE route, involving Cu III intermediates, is the energetically most favorable pathway for all the systems considered. Interestingly, the rate-determining step is the oxidative addition of the phenyl iodide to the metal center regardless of the nature of the heteroatom. The computed energy barriers in OA increase in the order O < S < NH. Using the Activation Strain Model (ASM) of chemical reactivity, it was found that the strain energy associated with the bending of the copper(I) complex controls the observed reactivity.

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Central bond in the three CN.cntdot.dimers NC-CN, CN-CN and CN-NC: electron pair bonding and Pauli repulsion effects

Cited by 196 publications

References 5 publications

Pyridine-Derived N-Heterocyclic Carbenes: An Experimental and Theoretical Evaluation of the Bonding in and Reactivity of Selected Normal and Abnormal Complexes of Nickel(II) and Palladium(II)

Pyridine-Derived N-Heterocyclic Carbenes: An Experimental and Theoretical Evaluation of the Bonding in and Reactivity of Selected Normal and Abnormal Complexes of Nickel(II) and Palladium(II)

The Case for Steric Repulsion Causing the Staggered Conformation of Ethane

Understanding the Heteroatom Effect on the Ullmann Copper-Catalyzed Cross-Coupling of X-Arylation (X = NH, O, S) Mechanism

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