Nature of the Te⋯N intramolecular interaction in organotellurium compounds. A theoretical investigation by NBO and AIM methods

Behera, Raghu Nath; Panda, Arunashree

doi:10.1016/j.comptc.2012.08.040

Cited by 13 publications

(11 citation statements)

References 85 publications

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“…The combination of AIM, NCI, and ELI‐D thus allows the monitoring of minute electronic changes in the Te–N interaction, which is dominated by covalent bonding aspects for short Te–N distances and ionic bonding aspects for longer Te–N distances. These calculations extend previous computational studies on intramolecularly coordinated N‐donor tellurium compounds by us and others , …”

Section: Introductionsupporting

confidence: 88%

Intramolecularly Coordinated 2‐Iminomethylphenyltellurium Compounds

et al. 2017

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Procedures for the synthesis of 2-(tBuNCH)-C 6 H 4 Te(S 2 CNEt 2 ) (1a), 2-(2′,6′-iPr 2 C 6 H 3 NCH)C 6 H 4 Te(S 2 CNEt 2 ) (1b), [2-(tBuNCH)C 6 H 4 ] 2 Te (2a), 2-(tBuNCH)C 6 H 4 TeCl (3a), and 2-(tBuNCH)C 6 H 4 TeCl 3 (4a) have been developed. Compounds 1a-4a possess 2-iminomethylphenyl groups that provide intramolecular N donation to the Te atoms, which was investigated by multinuclear NMR spectroscopy and X-ray crystallography. The Te-N bond lengths increase in the order 3a [2.203 (2) Å] < 4a [2.286(1) Å] < 1b [2.337(2) Å] < 1a [2.407(2) Å] < 2a [a] 3435 Scheme 1. Tellurium compounds stabilized by intramolecular N(sp 3 ) donation (top row) and N(sp 2 ) donation (bottom row). Full PaperScheme 2. General route for the synthesis of 2-iminomethylphenyltellurium compounds reported in the literature. analyzed through DFT calculations and real-space bonding indicators (RSBI), which are derived from the computed electron and pair densities. Topological dissection of the electron density (ED) according to the atoms-in-molecules (AIM) space-partitioning scheme [88] provides a bond-path motif that resembles the molecular structure as well as details of atomic properties such as charges and volumes. Analysis of the reduced density gradient, s(r) = [1/2(3π 2 ) 1/3 ]|∇ρ|/ρ 4/3 , according to the recently introduced noncovalent interactions (NCI) index [89] affords noncovalent bonding aspects. Notably, the assignment of different contact types, including steric/repulsive (λ 2 > 0), van der Waals like (λ 2 ≈ 0), and attractive (λ 2 < 0) interactions is facilitated by mapping the product of the ED and the sign of the second eigenvalue of the Hessian [sign(λ 2 )ρ] on the isosurfaces of s(r). Finally, topological dissection of the pair density according to the electron localizability indicator (ELI-D) [90] provides core, bonding, and lone-pair basins, which are especially valuable for the analysis of covalent (including dative) bonds. ELI-D isosurfaces (localization domain representations of the basins) and NCI isosurfaces show a complementary spatial distribution, [91] which suggests spatial separation of covalent and noncovalent bonding aspects, which has been a matter of recent debate. [92] The combination of AIM, NCI, and ELI-D thus allows the monitoring of minute electronic changes in the Te-N interaction, which is dominated by covalent bonding aspects for short Te-N distances and ionic bonding aspects for longer Te-N distances. These calculations extend previous computational studies on intramolecularly coordinated N-donor tellurium compounds by us [93] and others. [94,95] Scheme 3. Synthesis of 1a-4a and 1b.

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Section: Introductionsupporting

confidence: 88%

Intramolecularly Coordinated 2‐Iminomethylphenyltellurium Compounds

et al. 2017

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“…[21] Among the different chalcogenide derivatives, benzo-2,1,3-telluradiazoles have certainly attractedt he greatest interest because of their unique ribbon-like self-organization in the solid state (Figure 1a)f ormedt hrough strong N···TeS BIs (2.682(7)-2.720 (7) ). [4,[28][29][30][31] Although of great potential, these molecular systemsh ave remained confined to the fundamentalr esearch because of their thermali nstability and aptitude to undergo hydrolysis under ambient conditions.…”

Section: Introductionmentioning

confidence: 99%

“…Considering the experimental evidences and the theoretical studies, strong SBIs can be expected when descending in the chalcogen group, with the Te‐derived compounds establishing the strongest interactions . Among the different chalcogenide derivatives, benzo‐2,1,3‐telluradiazoles have certainly attracted the greatest interest because of their unique ribbon‐like self‐organization in the solid state (Figure a) formed through strong N⋅⋅⋅Te SBIs (2.682(7)–2.720(7) Å) . Although of great potential, these molecular systems have remained confined to the fundamental research because of their thermal instability and aptitude to undergo hydrolysis under ambient conditions.…”

Section: Introductionmentioning

confidence: 99%

Supramolecular Wiring of Benzo‐1,3‐chalcogenazoles through Programmed Chalcogen Bonding Interactions

Kremer

Fermi

Biot

et al. 2016

Chemistry A European J

115

112

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The high-yielding synthesis of 2-substituted benzo-1,3-tellurazoles and benzo-1,3-selenazoles through a dehydrative cyclization reaction has been reported, giving access to a large variety of benzo-1,3-chalcogenazoles. Exceptionally, these aromatic heterocycles proved to be very stable and thus very handy to form controlled solid-state organizations in which wire-like polymeric structures are formed through secondary N⋅⋅⋅Y bonding interactions (SBIs) engaging the chalcogen (Y=Se or Te) and nitrogen atoms. In particular, it has been shown that the recognition properties of the chalcogen centre at the solid state could be programmed by selectively barring one of its σ-holes through a combination of electronic and steric effects exerted by the substituent at the 2-position. As predicted by the electrostatic potential surfaces calculated by quantum chemical modelling, the pyridyl groups revealed to be the stronger chalcogen bonding acceptors, and thus the best ligand candidate for programming the molecular organization at the solid state. In contrast, the thiophenyl group is an unsuitable substituent for establishing SBIs in this molecular system as it gives rise to chalcogen-chalcogen repulsion. The weaker chalcogen donor properties of the Se analogues trigger the formation of feeble N⋅⋅⋅Se contacts, which are manifested in similar solid-state polymers featuring longer nitrogen-chalcogen distances.

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“…NBO analysis provides an efficient method to investigate intra‐ and intermolecular bondings and interactions, and also provides a convenient basis to investigate charge transfer or conjugative interactions in molecular systems, in terms of a set of occupied Lewis and unoccupied non‐Lewis localized orbitals. Stabilization energies ΔE, proportional to NBO interacting intensities, can be evaluated by using second‐order perturbation theory.…”

Section: Resultsmentioning

confidence: 99%

Structure and detonation performance of a novel HMX/LLM‐105 cocrystal explosive

Lin

Zhu

et al. 2013

J of Physical Organic Chem

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Intermolecular interactions and properties of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) / 2,6-diamino-3,5dinitropyrazine-1-oxide (LLM-105) cocrystal were studied by using the dispersion-corrected density functionals (ωB97XD, B97D) and meta-hybrid functional (M062x) methods. Binding energies, heats of formation, thermodynamic properties, atoms in molecules, and natural bond orbital analysis were performed to investigate HMX/LLM-105 complexes. Results show that the main intermolecular interactions between HMX and LLM-105 are CH…O, NH…O, N…O, and O…O interactions. In addition, Monte Carlo simulation was employed to predict the crystal structure of HMX/LLM-105 cocrystal. The HMX/LLM-105 cocrystal is most likely to crystallize in C2/c space group, and its corresponding cell parameters are Z = 8, a = 41.63 Å, b = 6.77 Å, c = 45.63 Å, ß = 164.55°, and ρ = 1.99 g/cm 3 . Detonation velocity and pressure of HMX/LLM-105 cocrystal are 8.95 km/s, 37.69GPa, a little lower than those of HMX (9.10 km/s, 37.76GPa). However, according to the net charges of nitro group, HMX/LLM-105 cocrystal exhibits less sensitive than HMX. Finally, bond dissociation energy calculation shows that HMX/LLM-105 complexes are thermally stable. Considering thermal stability, sensitivity, and detonation performance, HMX/LLM-105 cocrystal meets the requirements of insensitive high energy density materials.

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Nature of the Te⋯N intramolecular interaction in organotellurium compounds. A theoretical investigation by NBO and AIM methods

Cited by 13 publications

References 85 publications

Intramolecularly Coordinated 2‐Iminomethylphenyltellurium Compounds

Intramolecularly Coordinated 2‐Iminomethylphenyltellurium Compounds

Supramolecular Wiring of Benzo‐1,3‐chalcogenazoles through Programmed Chalcogen Bonding Interactions

Structure and detonation performance of a novel HMX/LLM‐105 cocrystal explosive

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