Theoretical analysis of bonding properties in 1,1-dicyanocyclopentane and 1,1-dichlorocyclopentane by applying the AIM and NBO approaches

Dakkouri, Marwan; Typke, V.

doi:10.1007/s11224-007-9159-9

Cited by 4 publications

(3 citation statements)

References 32 publications

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“…Such a sign inversion of the Laplacian means, however, that regardless of the extension of the basis set by simply employing a double zeta instead of triple zeta basis set, the C≡N bond character changes from a covalent to an ionic type, which is at least questionable and even absurd. This conspicuous dependency of the topological properties of the C≡N bond on the basis set confirms the results that we previously discussed [90] but contradicts the conclusion that was drawn earlier by Aray et al [91], asserting that the topological properties of the C≡N and the R-CN bonds are minimally affected by the variation of the basis set. Accordingly, further investigations should be conducted to explore whether other electron-rich bonds in different molecular surroundings show similar striking behavior and dependency on the quality of the basis set.…”

Section: Aim Analysissupporting

confidence: 73%

A Theoretical Investigation of Novel Sila- and Germa-Spirocyclic Imines and Their Relevance for Electron-Transporting Materials and Drug Discovery

Dakkouri

2023

Molecules

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A new class of spirocyclic imines (SCIs) has been theoretically investigated by applying a variety of quantum chemical methods and basis sets. The uniqueness of these compounds is depicted by various peculiarities, e.g., the incidence of planar six-membered rings each with two imine groups (two π bonds) and the incorporation of the isosteres carbon, silicon, or germanium spiro centers. Additional peculiarities of these novel SCIs are mirrored by their three-dimensionality, the simultaneous occurrence of nucleophilic and electrophilic centers, and the cross-hyperconjugative (spiro-conjugation) interactions, which provoke charge mobility along the spirocyclic scaffold. Substitution of SCIs with strong electron-withdrawing substituents, like the cyano group or fluorine, enhances their docking capability and impacts their reactivity and charge mobility. To gain thorough knowledge about the molecular properties of these SCIs, their structures have been optimized and various quantum chemical concepts and models were applied, e.g., full NBO analysis and the frontier molecular orbitals (FMOs) theory (HOMO-LUMO energy gap) and the chemical reactivity descriptors derived from them. For the assessment of the charge density distribution along the SCI framework, additional complementary quantum chemical methods were used, e.g., molecular electrostatic potential (MESP) and Bader’s QTAIM. Additionally, using the aromaticity index NICS (nuclear independent chemical shift) and other criteria, it could be shown that the investigated cross-hyperconjugated sila and germa SCIs are spiro-aromatics of the Heilbronner Craig-type Möbius aromaticity.

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Section: Aim Analysissupporting

confidence: 73%

A Theoretical Investigation of Novel Sila- and Germa-Spirocyclic Imines and Their Relevance for Electron-Transporting Materials and Drug Discovery

Dakkouri

2023

Molecules

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“…Dakkouri and Typke [168] used Bader's quantumtopological theory of atoms in molecules (AIM) and Weinhold's Natural Bond Orbital (NBO) analysis to study bonding properties in 1,1-dicyanocyclopentane and 1,1-dichlorocyclopentane. Some of the results were compared and verified by carrying out AIM and NBO calculations on various related cyclic and non-cyclic compounds.…”

Section: Issuementioning

confidence: 99%

Interplay of thermochemistry and Structural Chemistry, the journal (volume 18, 2007) and the discipline

Ponikvar

Liebman

2008

Struct Chem

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In this study, we relate the contents of the journal Structural Chemistry for the calendar year 2007 and thermochemistry. The year's articles were briefly summarized and a thermochemical comment written to supplement them. Frequently questions were asked and future research was suggested.Keywords Structural Chemistry Á Thermochemistry Á Thermodynamics Á Enthalpy of formation Á Enthalpy of phase change Á Enthalpy of reaction As practiced disciplines, structural chemistry and thermochemistry are very often unrelated. In this study, these disciplines are linked as relations are explicitly made using the contents of the journal Structural Chemistry (Vol. 18) for the calendar year 2007 as a scaffold for our analysis, for our selected articles in the discipline of structural chemistry. These studies have been reviewed by us, where we give them a thermochemical flavor. While this commentary is most generally written in terms of brief summaries of literature papers involving enthalpies of formation and/or reaction, not uncommonly we raise questions and even suggest possible future research. We are not, however, going to give a thermochemical slant on book reviews, honorary dedications, and obituaries although these works will be cited in our text.As such, this article is a sequel to our earlier related reviews of Structural Chemistry for the calendar years 2000 through 2004 [1-5]. Reviews for 2005 and 2006 are currently being prepared. Issue 1In the first article in the first issue of Structural Chemistry for 2007, Hargittai [6] asserted that while research is currently usually carried out in big groups, the most important ideas, observations and discoveries still belong to individuals who have to bring down dogmas or open entirely new areas in science. This may bring solace to the thermochemical community in which research groups are generally small, and the number of new practitioners sadly few.In the past decade, the crystal engineering of multidimensional arrays and networks containing metal ions has achieved considerable progress because of the increased interest in the potential utility of these compounds as zeolite-like materials [7-11], catalysts [12], or magnetic materials [13][14][15]. The thermochemistry of these species is complicated by their inherent complexity: however, estimation approaches of their key thermochemical quantities are increasingly reliable [16]. In the second article of this issue, by Wang et al. [17], the versatility of malonate dianion as a ligand for the construction of extended networks with different topologies dependent on the coordination geometry of the metal ion was discussed. The synthesis and structure of a novel malonate-bridged copper(II) compound in which copper(II) ions have two different coordination environments in a novel three-dimensional (3D) network was described. Metal malonates have been studied from a

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“…Recently we published a series of papers on the molecular structures and bonding properties of 1,1 disubstituted cyclopentanes [1][2][3][4]. One of the main results of these investigations was the successful combination of the experimental method of gasphase electron diffraction with ab initio calculations to determine a molecular structure which is consistent with the large amplitude motion present in five-membered rings, the pseudorotation.…”

Section: Introductionmentioning

confidence: 99%

The molecular structure of 1,1-dichlorosilacyclopentane as obtained from gas-phase electron diffraction and ab initio calculations

Dakkouri

Typke

2010

Journal of Molecular Structure

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Theoretical analysis of bonding properties in 1,1-dicyanocyclopentane and 1,1-dichlorocyclopentane by applying the AIM and NBO approaches

Cited by 4 publications

References 32 publications

A Theoretical Investigation of Novel Sila- and Germa-Spirocyclic Imines and Their Relevance for Electron-Transporting Materials and Drug Discovery

A Theoretical Investigation of Novel Sila- and Germa-Spirocyclic Imines and Their Relevance for Electron-Transporting Materials and Drug Discovery

Interplay of thermochemistry and Structural Chemistry, the journal (volume 18, 2007) and the discipline

The molecular structure of 1,1-dichlorosilacyclopentane as obtained from gas-phase electron diffraction and ab initio calculations

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