Chemical Bonds without “Chemical Bonding”? A Combined Experimental and Theoretical Charge Density Study on an Iron Trimethylenemethane Complex

Farrugia, Louis J.; Evans, Cameron; Tegel, Marcus

doi:10.1021/jp061846d

Cited by 164 publications

(153 citation statements)

References 73 publications

(100 reference statements)

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“…Indeed, one of the most interesting and non-intuitive topological structures within the QTAIM theory is the non-nuclear attractor, and just recently an experimental characterization of such an entity was carried out using X-ray diffraction density with 1.1 Å -1 resolution. 14 The literature accounts for various studies [15][16][17] dealing with experimental QTAIM charges from both ab initio procedures and X-ray densities and, in general, they are in good agreement with chemical insight.…”

Section: Introductionmentioning

confidence: 86%

Review of Experimental GAPT and Infrared Atomic Charges in Molecules

Richter¹,

Duarte²,

Silva³

et al. 2016

Journal of the Brazilian Chemical Society

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This review contains experimental values of polar tensors and generalized atomic polar tensor (GAPT) charges determined since the publication of the polar tensor formulism for infrared intensity interpretation in 1961. GAPT charges, also called mean dipole moment derivatives, for 167 atoms of 67 molecules are discussed and compared with infrared charges also determined completely from experimental intensities. The importance of the charge transfer and polarization dynamic contributions to the GAPT charge are emphasized as they differentiate this charge from most theoretically calculated charges. The inclusion of these dynamic contributions is shown to be necessary to provide adequate numerical descriptions of core electron ionization energy processes. These contributions are expected to be important in studies of chemical reactivity.

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Section: Introductionmentioning

confidence: 86%

Review of Experimental GAPT and Infrared Atomic Charges in Molecules

Richter¹,

Duarte²,

Silva³

et al. 2016

Journal of the Brazilian Chemical Society

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“…For a hydrogen bond system, in most cases, there is a bond path connecting the H to the Y atom and a (3,-1) bond critical point is found [181][182][183][184]. There has been a debate [185][186][187][188][189][190][191] about the usefulness of a (3,-1) critical point between two atoms to establish the presence or absence of a bond between the two atoms. One concern is that a bond critical point could be found for non-equilibrium geometries such as transition states, i.e., saddle points, rather than true global minima.…”

Section: Theoretical/computational Methodsmentioning

confidence: 99%

Defining the hydrogen bond: An account (IUPAC Technical Report)

Arunan

Desiraju

Klein³

et al. 2011

Pure and Applied Chemistry

880

605

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Abstract:The term "hydrogen bond" has been used in the literature for nearly a century now. While its importance has been realized by physicists, chemists, biologists, and material scientists, there has been a continual debate about what this term means. This debate has intensified following some important experimental results, especially in the last decade, which questioned the basis of the traditional view on hydrogen bonding. Most important among them are the direct experimental evidence for a partial covalent nature and the observation of a blue-shift in stretching frequency following X-HؒؒؒY hydrogen bond formation (XH being the hydrogen bond donor and Y being the hydrogen bond acceptor). Considering the recent experimental and theoretical advances, we have proposed a new definition of the hydrogen bond, which emphasizes the need for evidence. A list of criteria has been provided, and these can be used as evidence for the hydrogen bond formation. This list is followed by some characteristics that are observed in typical hydrogen-bonding environments.

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“…Numerous cases exist, however, where either (i) classical chemists expect a bonding interaction (or it is shown through other methods, such as energy decomposition schemes) but no AIL is present [15], or (ii) steric repulsion is believed to exist, but an AIL is seen regardless [16][17][18][19][20][21][22][23][24][25][26]. These problem cases have resulted in a very long debate, questioning on one hand the validity and interpretation of QTAIM results [27][28][29][30][31] and on the other hand the nature of classical chemical concepts, such as steric repulsion [32][33][34][35][36].…”

Section: Introductionmentioning

confidence: 99%

Evaluating common QTAIM and NCI interpretations of the electron density concentration through IQA interaction energies and 1D cross-sections of the electron and deformation density distributions

Cukrowski

Lange

Adeyinka

et al. 2015

Computational and Theoretical Chemistry

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Highlights• Classical steric clashes might have the same topological features as bonding interactions.• An AIL can be observed for highly attractive or repulsive interactions.• An AIL might be a result of either an inflow or outflow of density.• Locally accumulated density does not imply an attractive interaction or an inflow of density.• Nature of an interaction can change with molecular environment. Graphical abstract 2 AbstractNine kinds of inter-and intramolecular interactions were investigated by exploring the topology of electron density in the interatomic regions using standard protocols of QTAIM, IQA and NCI techniques as well as in-house developed cross-sections of the electron and deformation density distributions. The first four methods provide the properties of the resultant density distribution in a molecular system whereas the later illustrates the process, inflow or outflow of density from fragments to the interatomic region of an interaction on its formation in a molecular system. We used (i) the QTAIM-defined atomic interaction line, AIL (presence or absence), (ii) IQA-defined interaction energy, attractive to repulsive, (ii)  2 < 0 to  2 >0, or (iii) (r) > 0 to (r) < 0; hence, none of the topological indices used here, either separately or combined, can be used to definitely predict the (de)stabilizing nature of an interaction except highly repulsive ones for which the absence of AIL, interatomic density depletion and outflow of density on interaction formation are observed.

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Chemical Bonds without “Chemical Bonding”? A Combined Experimental and Theoretical Charge Density Study on an Iron Trimethylenemethane Complex

Cited by 164 publications

References 73 publications

Review of Experimental GAPT and Infrared Atomic Charges in Molecules

Review of Experimental GAPT and Infrared Atomic Charges in Molecules

Defining the hydrogen bond: An account (IUPAC Technical Report)

Evaluating common QTAIM and NCI interpretations of the electron density concentration through IQA interaction energies and 1D cross-sections of the electron and deformation density distributions

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