Aspects of the chemistry of diorgano tritellurides

Maslakov, A. G.; Greaves, Martin R.; McWhinnie, William R.; McWhinnie, Sean L. W.

doi:10.1016/0022-328x(94)80040-5

Cited by 7 publications

(3 citation statements)

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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 .…”

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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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Section: Introductionmentioning

confidence: 99%

Intramolecularly Coordinated 2‐Iminomethylphenyltellurium Compounds

et al. 2017

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“…Although a rational synthesis was developed by the reaction of organotellurenyl(II) halides with telluride ions, the number of structurally characterized diorgano tritellurides is still limited to two examples, , and their reactivity remains unexplored. Our interest in organotelluroxane chemistry required the preparation of (8-dimethylaminonaphthyl) ditelluride ( 1 ), for which we used a procedure similar to that already published by Singh et al Thus, the reaction of 8-dimethylamino-1-naphthyllithium diethyl etherate with Te powder in THF followed by vigorous air oxidation for 10 min provided a reaction mixture consisting of a deeply colored solution containing the ditelluride RTeTeR ( 1 ) and the tritelluride RTeTeTeR ( 2 ) in varying ratios (R = 8-Me 2 NC 10 H 6 ).…”

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“…In light of the limited stability of tritellurides in solution at room temperature and the established 125 Te NMR parameters of 1 and 2 , we propose that the second of the two 125 Te NMR chemical shifts reported for bis-2-( p -tolyliminomethyl)phenyl tritelluride (δ = 740.5 and 432.1) is erroneously assigned and due to the corresponding ditelluride. In an effort to suppress the decomposition, a low-temperature 125 Te NMR spectrum of an analytically pure crystalline sample of 2 was recorded in CD 2 Cl 2 at −90 °C (acquisition time 2 h), which is shown in Figure . The spectrum shows two slightly shifted signals at δ = 703.5 and −294.7 with an integral ratio of 2:1 for the tritelluride 2 .…”

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New Insights into the Formation and Structure of Diaryl Tritellurides

2009

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The reaction of 8-dimethylamino-1-naphthyllithium diethyl etherate with tellurium powder and subsequent O 2 oxidation was reinvestigated. Besides the previously reported bis[8-(dimethylamino)naphthyl] ditelluride (1), the new bis[8-(dimethylamino)naphthyl] tritelluride (2) was isolated in 42% yield and fully characterized. Low-temperature 125 Te NMR spectroscopy provides evidence to suggest that analytically pure 2 is in equilibrium with 1 and bis[8-(dimethylamino)naphthyl] tetratelluride (2a).

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A Summary of Functional Groups Containing Selenium and Tellurium: A Catalog of the Many Groups that are Known and Some that are Not

Hack

Liebman

2013

Patai's Chemistry of Functional Groups

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In the current chapter we provide a catalog of functional groups containing the chalcogens selenium and tellurium where by functional group we mean the central atom, Se or Te, and its local arrangement of atoms bonded to it by single or multiple bonds (its neighborhood). We will do so by cataloging examples of compounds containing the groups. The atoms that define the local neighborhood are limited here to H, C, N, the chalcogens O, S, Se, Te, and the halogens F, Cl, Br and I. As such we avoid Se‐ and Te‐bonding to metals and metalloids and so we will ignore all salts, and we also ignore all groups with formal charges. However arbitrarily, we did include complexes involving species wherein, with appropriate bond‐shifting, we can draw the compound of interest without any formal charges. We have also avoided mention of free radicals and other species with unpaired electrons. All of the groups were explicitly chosen, and have at least one carbon attached to the selenium or tellurium. For each group we generally give one compound as an example (admittedly our choice of name is often unsystematic), a reference to the primary literature (again chosen unsystematically), and the CAS RN for the example compound (when available). Where there is no example we will generally explicitly say so, occasionally with due annotation as NO CAS RN or “no compounds identified” to encourage their study.

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Aspects of the chemistry of diorgano tritellurides

Cited by 7 publications

References 9 publications

Intramolecularly Coordinated 2‐Iminomethylphenyltellurium Compounds

Intramolecularly Coordinated 2‐Iminomethylphenyltellurium Compounds

New Insights into the Formation and Structure of Diaryl Tritellurides

A Summary of Functional Groups Containing Selenium and Tellurium: A Catalog of the Many Groups that are Known and Some that are Not

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