The aromaticity and electronic properties of monosubstituted benzene, borazine and diazadiborine rings: an ab initio MP2 study

Srivastava, Ambrish Kumar; Pandey, Sarvesh Kumar; Misra, Neeraj

doi:10.1007/s00214-016-1918-5

Cited by 12 publications

(6 citation statements)

References 30 publications

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“…The decrease in aromaticity can be expected due to Li-substitution. This feature has already been in some mono-substituted benzene [3,4]. Therefore, our calculated NICS and PDI values clearly suggest that all lithiated analogues are indeed aromatic however their degree of aromaticity is lower than corresponding hydrocarbons.…”

Section: Resultssupporting

confidence: 74%

“…This is why the whole chemistry of benzene is based on substitution reaction in which an atom or group usually replaces hydrogen attached to the ring. The substitution causes to significantly affect the chemical reactivity of the ring as noticed in many studies [2][3][4]. This may results in reducing the ionization energy or increasing the electron affinity of the substituted rings.…”

Section: Introductionmentioning

confidence: 96%

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Organic superalkalis with closed-shell structure and aromaticity

Srivastava

2018

Molecular Physics

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Benzene (C 6 H 6 ) and polycyclic hydrocarbons such as naphthalene (C 10 H 8 ), anthracene (C 14 H 10 ) and coronene (C 24 H 12 ) are well known aromatic organic compounds. We study the substitution of Li replacing all H atoms in these hydrocarbons using density functional method. The vertical ionization energy (VIE) of such lithiated species, i.e., C 6 Li 6 , C 10 Li 8 , C 14 Li 10 and C 24 Li 12 ranges 4.24-4.50 eV, which is lower than the IE of Li atom. Thus, these species may behave as superalkalis, due to their lower IE than alkali metal. However, these lithiated species possess planar and closed-shell structure, unlike typical superalkalis.Furthermore, all Li-substituted species are aromatic although their degree of aromaticity is reduced as compared to corresponding hydrocarbon analogues. We have further explored the structure of C 6 Li 6 as star-like, unlike its inorganic analogue B 3 N 3 Li 6 , which appears as fanlike structure. We have also demonstrated that the interaction of C 6 Li 6 with a superhalogen (such as BF 4 ) is similar to that of a typical superalkali (such as OLi 3 ). This may further suggest that the proposed lithiated species may form a new class of closed-shell organic superalkalis with aromaticity.

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Section: Resultssupporting

confidence: 74%

Section: Introductionmentioning

confidence: 96%

Organic superalkalis with closed-shell structure and aromaticity

Srivastava

2018

Molecular Physics

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“…Notably, dianionic 4 0 also bears a planar B 4 N 2 ring, which is in stark contrast to the twisted ring framework experimentally observed for 4, implying the impact of substituents at the B and N atoms on the skeletal geometry. 30,[32][33][34][35][36] The selected p-type molecular orbitals (p-MOs) of 3 0 and 4 0 are summarized in Fig. 2.…”

Section: Methodsmentioning

confidence: 99%

“…The substituent effect on the aromaticity in benzene as well as in borazine has been reported. [30][31][32][33][34][35][36] According to those prior studies, while the aromaticity of benzene resists substituent inuences, that of borazine is signicantly affected by the nature of substituents. In borazine, generally the electron-donating group (EDG) on B decreases the aromaticity, although electron-withdrawing group (EWG) on B and both EDG and EWG on N lead to the pronounced aromaticity.…”

Section: Introductionmentioning

confidence: 99%

Aromatic nature of neutral and dianionic 1,4-diaza-2,3,5,6-tetraborinine derivatives

Ota

Kinjo

2021

RSC Adv.

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“…As displayed in Fig.1, the lowest energy structure of B 3 N 3 H 5 Li corresponds to the one in which Li is substituted at N site. This can be expected due to strong interaction between electronegative N and electropositive Li, unlike B 3 N 3 H 5 X (X = OH, NO 2 , NH 3 , CH 3 , CF 3 ) which possesses lower energy with X substituted at B-site[32,33]. For substitution of two Li atoms, there are four possible isomers with relative energies 38.2−75.9 kcal/mol but in the lowest energy isomer of B 3 N 3 H 4 Li 2 , both Li atoms bind to N-sites.…”

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confidence: 99%

Alkalized borazine: A simple recipe to design closed‐shell superalkalis

Srivastava¹,

Tiwari²,

Misra

2017

Int J of Quantum Chemistry

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Superalkalis are hypervalent species, possessing smaller ionization energy (IE) than alkali metal.These species are typically designed by electronegative atoms with excess electropositive ligands.Typical examples include FLi 2 , OLi 3 , NLi 4 , etc. Herein, we study successive alkali metal substitution at H atoms in borazine (B 3 N 3 H 6 ). Our B3LYP and MP2 calculations demonstrate that the vertical ionization energy (VIE) of B 3 N 3 H 6-x Li x decreases with the increase in x for x 5 1-6. For x 4, the VIE of B 3 N 3 H 6-x Li x becomes lower than that of Li atom, thereby indicating their superalkali nature.More interestingly, all these species are planar with closed-shell structure such that the NICS zz value at the ring's center is reduced. We have also studied B 3 N 3 M 6 (M 5 Li, Na, and K) species and found that the VIE is further reduced in case of Na and K substitutions. These findings should suggest a simple yet effective route to the design of species with lower ionization energies than alkali metal.ab initio calculations, alkali substitution, borazine, ionization energy, superalkali 1 | I N TR ODU C TI ON During 1980s, the hypervalent species possessing lower ionization energy (IE) than alkali metals had been reported as superalkali species by Gutsev and Boldyrev. [1] They suggested a general formula of XM n11 for superalkalis, where M is alkali atom and X is electronegative atom with valence n.

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The aromaticity and electronic properties of monosubstituted benzene, borazine and diazadiborine rings: an ab initio MP2 study

Cited by 12 publications

References 30 publications

Organic superalkalis with closed-shell structure and aromaticity

Organic superalkalis with closed-shell structure and aromaticity

Aromatic nature of neutral and dianionic 1,4-diaza-2,3,5,6-tetraborinine derivatives

Alkalized borazine: A simple recipe to design closed‐shell superalkalis

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