Relation between resonance energy and substituent resonance effect in <i>P</i>‐phenols

Krygowski, Tadeusz M.; Stępień, Beata T.; Cyrański, Michał K.; Ejsmont, Krzysztof

doi:10.1002/poc.960

Cited by 35 publications

(30 citation statements)

References 43 publications

(24 reference statements)

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“…The obtained results for the retrieved data set ( Figure 6) confirm this suggestion, showing the range of HOMA values from 0.826 and in a more regular way between 0.88 and 1.00. A relatively small decrease in the aromatic character of the phenyl ring as an effect of the substituent is in line with more detailed studies based on QM modeling of this problem [42,43]. The obtained results for the retrieved data set ( Figure 6) confirm this suggestion, showing the range of HOMA values from 0.826 and in a more regular way between 0.88 and 1.00.…”

supporting

confidence: 77%

“…The obtained results for the retrieved data set ( Figure 6) confirm this suggestion, showing the range of HOMA values from 0.826 and in a more regular way between 0.88 and 1.00. A relatively small decrease in the aromatic character of the phenyl ring as an effect of the substituent is in line with more detailed studies based on QM modeling of this problem [42,43]. It is important to note that histograms of the data sets for para-substituted nitrobenzene derivatives and measurements with R ≤ 0.075 or 0.1 are characterized by similar shapes and statistical parameters as shown above; only a slightly greater range of variability of the studied parameters and their esds were observed.…”

mentioning

confidence: 63%

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Effect of Intra- and Intermolecular Interactions on the Properties of para-Substituted Nitrobenzene Derivatives

et al. 2016

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Abstract:To study the influence of intra-and intermolecular interactions on properties of the nitro group in para-substituted nitrobenzene derivatives, two sources of data were used: (i) Cambridge Structural Database and (ii) quantum chemistry modeling. In the latter case, "pure" intramolecular interactions were simulated by gradual rotation of the nitro group in para-nitroaniline, whereas H-bond formation at the amino group allowed the intermolecular interactions to be accounted for. BLYP functional with dispersion correction and TZ2P basis set (ADF program) were used to perform all calculations. It was found that properties of the nitro group dramatically depend on both its orientation with respect to the benzene ring as well as on the substituent in the para-position. The nitro group lies in the plane of the benzene ring for only a small number of molecules, whereas the mean value of the twist angle is 7.3 deg, mostly due to intermolecular interactions in the crystals. This distortion from planarity and the nature of para-substituent influence the aromaticity of the ring (described by HOMA index) and properties of the nitro group due to electronic effects. The results obtained by QM calculations fully coincide with observations found for the data set of crystal structures.

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supporting

confidence: 77%

“…The obtained results for the retrieved data set ( Figure 6) confirm this suggestion, showing the range of HOMA values from 0.826 and in a more regular way between 0.88 and 1.00. A relatively small decrease in the aromatic character of the phenyl ring as an effect of the substituent is in line with more detailed studies based on QM modeling of this problem [42,43]. It is important to note that histograms of the data sets for para-substituted nitrobenzene derivatives and measurements with R ≤ 0.075 or 0.1 are characterized by similar shapes and statistical parameters as shown above; only a slightly greater range of variability of the studied parameters and their esds were observed.…”

mentioning

confidence: 63%

Effect of Intra- and Intermolecular Interactions on the Properties of para-Substituted Nitrobenzene Derivatives

et al. 2016

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“…The role of the π* orbital energy becomes well evident by a close examination of both the chloride and bromide series. The trends of π* energies are 5a < 6a for the chlorides and 8 < 5b < 6b for the bromides [39,40]. This trend is exactly the opposite of that found for the α values.…”

Section: Aromatic Halidesmentioning

confidence: 51%

Electrocatalysis and electron transfer mechanisms in the reduction of organic halides at Ag

et al. 2009

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The reductive cleavage of a series of organic halides, including both aromatic and aliphatic compounds, has been investigated in acetonitrile at glassy carbon and silver electrodes. Ag exhibits extraordinary electrocatalytic activities for the reduction of most of the investigated halides. During the reductive cleavage of a carbon-halogen bond, electron transfer (ET) and bond breaking may occur either in a single step or in two distinct steps. The compounds examined in this study are representative of both dissociative electron transfer (DET) mechanisms. In general a link between the DET mechanism and electrocatalysis at Ag is observed for the whole set of data. There is no catalysis at all when the ET involves a substituent that gives a stable radical anion. Furthermore, there is no catalysis for all aromatic chlorides. Instead, a remarkable electrocatalysis is observed for all compounds undergoing a concerted DET mechanism, regardless of the nature of the halogen atom.

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“…Several methods for the calculation of magnetic-based aromaticities are introduced [13][14][15][16][17]. One of the most widely used indices is the Nucleus-Independent Chemical Shift (NICS), which is defined as the negative of magnetic shielding in a given point of the molecule [18].…”

Section: Introductionmentioning

confidence: 99%