Synthesis and characterization of [2-(2-phenyl-5,6-dihydro-4H-1,3-oxazinyl)] tellurenyl chloride

Kumar, Sangit; Singh, Harkesh B.; Wolmershäuser, G.

doi:10.1016/j.jorganchem.2005.04.006

Cited by 11 publications

(4 citation statements)

References 15 publications

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“…In the 125 Te NMR spectra, compounds 5 and 6 show single resonances at δ = 1318.5 and δ = 1274.3 ppm, respectively. Both these chemical shift values are in agreement with reported values for monoorganotellurenyl halides with an sp 2 N coordinating group, namely 2‐( t BuNCH)C 6 H 4 TeCl ( δ = 1258.6 ppm), [C 6 H 4 (C 5 H 8 NO)TeCl] ( δ = 1202.8 ppm), [C 6 H 4 (C 4 H 6 NO)TeCl] ( δ = 1226 ppm), [C 6 H 4 C=N(C 6 H 5 )TeBr] ( δ = 1316 ppm), [C 6 H 4 C=N(C 6 H 4 Me‐4)TeBr] ( δ = 1424 ppm) and [C 6 H 4 C=N(C 6 H 4 Me 2 ‐2,6)TeBr] ( δ = 1427 ppm) ,…”

Section: Resultssupporting

confidence: 90%

Exploring the Role of Strong Intramolecular Coordination of the 2‐(2'‐pyridyl)phenyl Group in Heavy Main Group Halides: Insights from Synthesis, Structural, and Bonding Analyses

et al. 2020

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By the transmetallation of ppyHgCl [ppy = 2‐(2'‐pyridyl)phenyl] (1) with SnCl4 and SbCl3, the synthesis of the monoorgano main group halides, [ppySnCl3(H2O)]·2(0.5diox) (diox = 1,4‐dioxane) [2(H2O)]·2(0.5diox) and [ppySbCl2] (3) was achieved. The reaction of 1 with BiCl3 does not give the analogous monoorganobismuth dichloride. Instead, it results in the formation of [(ppy)2Bi]+·[ppyBiCl3]– (4). Reactions of (ppy)2Te and (ppyTe)2 with SO2Cl2 and Br2 result in the formation of ppyTeCl (5) and ppyTeBr (6) respectively. All the synthesized compounds were characterized by multi‐nuclear NMR spectroscopy (1H, 13C, 119Sn, and 125Te), FT‐IR spectroscopy, ESI‐MS, CHN analysis, and single‐crystal X‐ray diffraction studies. The molecular structures of 2–6 reveal strong intramolecular coordination of the N‐atoms of the pendant arms with the main group element centers. DFT calculations; including Natural Bond Order (NBO), Electron Localization Function (ELF), Electrostatic Surface Potential (ESP) and Atoms in Molecules (AIM) infer that the stability of 2–6 relies on the σ‐hole participation of the element center with the N‐lone pair of the pyridyl arm.

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Section: Resultssupporting

confidence: 90%

Exploring the Role of Strong Intramolecular Coordination of the 2‐(2'‐pyridyl)phenyl Group in Heavy Main Group Halides: Insights from Synthesis, Structural, and Bonding Analyses

et al. 2020

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“…The stabilization of these tellurium compounds often relied on the judicious choice of aryl substituents containing intramolecularly coordinating N(sp 3 )‐donor ligands, such as the “one‐arm” 2‐dialkylaminomethylphenyl group ( I ), the “two‐arm” 2,6‐bis(dialkylaminomethylphenyl) group ( II ), and the “stiff‐arm” 8‐dialkylaminonaphthyl group ( III , Scheme ) , . These ligands are complemented by aryl substituents containing intramolecularly coordinating N(sp 2 )‐donor ligands, such as the 2‐pyridylphenyl group ( IV ), the 2‐oxazolinylphenyl group ( V ),, and the 2‐iminomethylphenyl group ( VI , Scheme ) , . The ligands I – V are usually prepared by N‐directed ortho ‐ or peri ‐lithiation of the aromatic systems through C–H/Li or C–Br/Li exchange reactions .…”

Section: Introductionmentioning

confidence: 99%

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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“…32 In X-1a-H, the Te-Br distances are slightly longer but the Te-Cl distances are much larger and fall at the long end of the range observed in cases in which the tellurium atom is engaged in intramolecular secondary bonding. [26][27][28][29][33][34][35][36] Each X-1a-H molecule is connected to a neighbor by hydrogen bonding to the halogen atom, which in turn is engaged in an interaction with the tellurium atom of the first molecule to a distance (d(Te···Cl) = 3.570, 3.656 Å, d(Te···Br) = 3.602, 3.693 Å) that is shorter than the Te-X sum of van der Waals radii (X = Cl: 3.81 Å, X = Br: 3.91 Å) but much longer than the corresponding single bond. These interactions propagate through the crystal forming infinite chains.…”

Section: Resultsmentioning

confidence: 99%

Influence of acidic media on the supramolecular aggregation of iso-tellurazole N-oxides

Lee

Jenkins

et al. 2016

Can. J. Chem.

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Iso-tellurazole N-oxides are promising supramolecular building blocks. While in neutral solutions, they form tetraand hexameric macrocyclic aggregates linked by Te···O secondary bonding ( hole interactions or chalcogen bonds), protonation of the oxygen atom in acidic media disrupts such supramolecular association. The process is reversible and, consequently, can be used to switch on and off the self-assembly process. Hammett acidity measurements gave pK a values of -3.2 for the protonated molecules. Adducts with HCl and HBr were isolated and structurally characterized. Protonation in solution led to the crystallization of a new polymorph of 3-methyl-5-phenyl-1,2-tellurazole N-oxide, which features a unique polymeric arrangement. Résumé :Les isotellurazoles N-oxydes sont des synthons supramoléculaires prometteurs. Bien qu'en solution neutre, ils forment des agrégats macrocycliques tétramériques et hexamériques retenus par des liaisons secondaires Te···O (interactions de trous ou liaisons chalcogène), en milieu acide, la protonation des atomes d'oxygène perturbe une association supramoléculaire de ce type. Ce processus d'association est réversible et peut donc être utilisé pour provoquer ou inhiber le processus d'autoassamblage. Nous avons calculé, pour les molécules protonées, une valeur de pK a de -3,2 dérivée des mesures de l'acidité en utilisant l'équation de Hammett. En outre, nous avons isolé des adduits de HCl et de HBr et en avons caractérisé les structures. La protonation en solution a entraîné la cristallisation d'un nouveau polymorphe du 3-méthyl-5-phényl-1,2-tellurazole N-oxyde présentant une structure polymérique unique. [Traduit par la Rédaction]Mots-clés : interactions de trous sigma, liaison secondaire, chalcogènes, chimie supramoléculaire, chimie du groupement principal.

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Synthesis and characterization of [2-(2-phenyl-5,6-dihydro-4H-1,3-oxazinyl)] tellurenyl chloride

Cited by 11 publications

References 15 publications

Exploring the Role of Strong Intramolecular Coordination of the 2‐(2'‐pyridyl)phenyl Group in Heavy Main Group Halides: Insights from Synthesis, Structural, and Bonding Analyses

Exploring the Role of Strong Intramolecular Coordination of the 2‐(2'‐pyridyl)phenyl Group in Heavy Main Group Halides: Insights from Synthesis, Structural, and Bonding Analyses

Intramolecularly Coordinated 2‐Iminomethylphenyltellurium Compounds

Influence of acidic media on the supramolecular aggregation of iso-tellurazole N-oxides

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