A DFT Study on the Stability and Aromaticity of Heterobenzenes Containing Group 15 Elements

Păușescu, Iulia; Medeleanu, Mihai; Ştefănescu, Mircea; Péter, Fráncisc; Pop, Raluca

doi:10.1002/hc.21250

Cited by 26 publications

(11 citation statements)

References 36 publications

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“…Among other criteria, it is known that nucleus-independent chemical shift values calculated 1 Å above the corresponding RCPs (NICS(1)), black dots in Figure , provide a good measure of the aromaticity/π electron delocalization along a ring. , Typical NICS(1) values, in parts per million, are ca. −10.2 for benzene, the paradigm of an aromatic ring, , −10.1 for pyridine, , and −10.8 (rings 1 and 2) and −8.4 (ring 4) for isolated phen . In this work, NICS(1) values for phen at [Re(PPh 2 ) (CO) 3 (phen)] (−10.1, −10.3, and −8.7 ppm for rings 1, 2, and 4 in Table S10, respectively) are similar to those mentioned above for the isolated ligand.…”

Section: Resultssupporting

confidence: 81%

Insights on the Reactivity of Terminal Phosphanido Metal Complexes toward Activated Alkynes from Theoretical Computations

Álvarez¹,

Mera‐Adasme

Riera

et al. 2017

Inorg. Chem.

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Herein we present a theoretical study on the reaction of [Re(PPh) (CO)(phen)] (phen = 1,10-phenanthroline) and [Re(PPh) (CO)(bipy)] (bipy = 2,2'-bipyridine) toward methyl propiolate. In agreement with experimental results for the phen ligand, the coupling of the substituted acetylenic carbon with the nonsubstituted ortho carbon of the phen ligand is the preferred route from both kinetic and thermodynamic viewpoints with a Gibbs energy barrier of 18.8 kcal/mol and an exoergicity of 11.1 kcal/mol. There are other two routes, the insertion of the acetylenic fragment into the P-Re bond and the coupling between the substituted acetylenic carbon and a carbonyl ligand in cis disposition, which are kinetically less favorable than the preferred route (by 2.8 and 1.9 kcal/mol, respectively). Compared with phen, the bipy ligand shows less electrophilic character and also less π electron delocalization due to the absence of the fused ring between the two pyridine rings. As a consequence, the route involving the coupling with a carbonyl ligand starts to be kinetically competitive, whereas the product of the attack to bipy is still the most stable and would be the one mainly obtained after spending enough time to reach thermal equilibrium.

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Section: Resultssupporting

confidence: 81%

Insights on the Reactivity of Terminal Phosphanido Metal Complexes toward Activated Alkynes from Theoretical Computations

Álvarez¹,

Mera‐Adasme

Riera

et al. 2017

Inorg. Chem.

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“…The stability and aromaticity are related concepts, and thus, some of the DFT descriptors can be discussed to analyze aromaticity. − Table lists the energies of the HOMO, the LUMO, energy gap ( E g ), vertical IP, and EA as well as η, S , χ, μ, and ω. From Table , it has been found that the keto form has the lowest HOMO–LUMO gap (2.30 eV) followed by enol forms (3.08 eV).…”

Section: Resultsmentioning

confidence: 99%

Structures, Energetics, and Spectra of (NH) and (OH) Tautomers of 2-(2-Hydroxyphenyl)-1-azaazulene: A Density Functional Theory/Time-Dependent Density Functional Theory Study

et al. 2022

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Tautomerization of 2-(2-hydroxyphenyl)-1-azaazulene ( 2OHPhAZ ) in the gas phase and ethanol has been studied using B3LYP, M06-2X, and ωB97XD density functional theory (DFT) with different basis sets. For more accurate data, energies were refined at CCSD(T)/6-311++G(2d,2p) in the gas phase. Nuclear magnetic resonance (NMR), aromaticity, Fukui functions, acidity, and basicity were also calculated and compared with experimental data. Time-dependent density functional theory (TDDFT)-solvation model based on density (TDDFT-SMD) calculations in acetonitrile have been utilized for the simulation of UV–vis electronic spectra. In addition, electronic structures of the investigated system have been discussed. The results reveal that the enol form ( 2OHPhAZ ) is thermodynamically and kinetically stable relative to the keto tautomer ( 2OPhAZ ) and different rotamers ( 2OHPhAZ–R1:R3 ) in the gas phase and ethanol. A comparison with the experiment illustrates a good agreement and supports the computational findings.

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“…Analogues of benzene where one CH group is formally replaced by a main group element are well known and in many cases have been shown to retain a significant degree of aromatic character . Some notable examples from recent years include bisma‐, alumina‐, sila‐, germa‐ and stannabenzenes …”

Section: Metallabenzenesmentioning

confidence: 99%

Recent Advances in Metallaaromatic Chemistry

Frogley

Wright

2017

Chemistry A European J

145

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Metallaaromatics can be broadly defined as aromatic compounds in which one of the ring atoms is a transition metal. The metallabenzenes are one important class of these compounds that has undergone extensive study recently. Closely related species such as fused-ring metallabenzenes, heterometallabenzenes, π-coordinated metallabenzenes and metallabenzynes have also attracted considerable attention. Although many metallaaromatics can be considered as metalla-analogues of classic organic aromatic compounds, this is not always the case. Recent seminal studies have shown that metallapentalenes and metallapentalynes, which are metalla-analogues of the anti-aromatic compounds pentalene and pentalyne, are in fact aromatic and highly stable. Very unusual spiro-metallaaromatic compounds have also recently been isolated. In this concepts article, key features of all these intriguing metallaaromatic compounds are discussed with reference to the structural, spectroscopic, reactivity and theoretical studies that have been undertaken. These compounds continue to generate much interest, not only because of the contributions they make to fundamental chemical understanding, but also because of the promise of possible practical applications.

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A DFT Study on the Stability and Aromaticity of Heterobenzenes Containing Group 15 Elements

Cited by 26 publications

References 36 publications

Insights on the Reactivity of Terminal Phosphanido Metal Complexes toward Activated Alkynes from Theoretical Computations

Insights on the Reactivity of Terminal Phosphanido Metal Complexes toward Activated Alkynes from Theoretical Computations

Structures, Energetics, and Spectra of (NH) and (OH) Tautomers of 2-(2-Hydroxyphenyl)-1-azaazulene: A Density Functional Theory/Time-Dependent Density Functional Theory Study

Recent Advances in Metallaaromatic Chemistry

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