Lewis acid and Lewis base behaviour of a tellurium(II) compound: a mercury(II) complex of a bis-telluride ligand with a 13-member macrocyclic chelate ring

Al-Salim, Najih I.; Hamor, T. A.; McWhinnie, William R.

doi:10.1039/c39860000453

Cited by 41 publications

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“…The geometry of the HgX 2 Te 2 units in these complexes is distorted tetrahedral. The angular distortion around the central Hg(II) atom in 2a is limited over a small range, 100.16(5)-117.11(5)°and values of the bond angles Cl-Hg-Cl, 108.19(7)°and Te-Hg-Te, 108.67 (2) to the corresponding values reported for the HgCl 2 complex of chelating bis(telluride), 1,6-bis(2-butyltellurophenyl)-2,5-diazahexa-1,5-diene [15]. The HgBr 2 Te 2 unit in 3c comprises of two symmetry related (i = Àx, y, À0.5 À z) halves with Hg-Br and Hg-Te bond distances of 2.656(2) and 2.797(3) Å , respectively.…”

Section: Crystal Structures Of 2a and 3cmentioning

confidence: 73%

Structural characterization of rare intramolecularly (1,4-Te⋯N) bonded diorganotellurides and their monomeric complexes with mercury(II) halides: Metal assisted C–H⋯X (Hg) interactions leading to supramolecular architecture

Chauhan

Anamika

Kumar

et al. 2006

Journal of Organometallic Chemistry

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Section: Crystal Structures Of 2a and 3cmentioning

confidence: 73%

Structural characterization of rare intramolecularly (1,4-Te⋯N) bonded diorganotellurides and their monomeric complexes with mercury(II) halides: Metal assisted C–H⋯X (Hg) interactions leading to supramolecular architecture

Chauhan

Anamika

Kumar

et al. 2006

Journal of Organometallic Chemistry

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“…2-(2-Pyridyl)phenyltellurium(1v) tribromide (1.04 g, 2 mmol) and 2-(2-pyridyl)phenylmercury(I1) chloride (0.78 g, 2 mmol) were dissolved in dry 1,4-dioxane (20 cm3) and refluxed for 3 h. The white solid thus formed was filtered off and washed with dry methanol, followed by recrystallisation from nitromethane, m.p. 235-238 "C. Analysis indicated the composition C,,H, ,Br3CI-HgN,Te (Found: C , 29.3; H, 1.80; N,3.10. C,,H1,Br,C1HgN,Te requires C,29.0;H,1.75;N,3.05%).…”

Section: Reuction Of Bis[2-(2-pyridylmentioning

confidence: 99%

2-Pyridyl- and quinolin-2-yl-functionalised organyltellurium ligands. The stabilisation of diorganyl tritellurides. The crystal and molecular structures of 2-(2-pyridyl)phenyltellurium(IV) tribromide, dimethyldithiocarbamato[2-(2-pyridyl)phenyl]tellurium(II), and p-ethoxyphenyl 2-(2-pyridyl)phenyl telluride

Al-Salim¹,

West²,

McWhinnie³

et al. 1988

J. Chem. Soc., Dalton Trans.

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The syntheses and spectroscopic data (13C n.m.r.) for some new organyltellurium ligands are described. Thus trans metallation of 2-(2-pyridy1)phenyl-(R) or 2-(quinolin-2-yl)phenyI-(R') mercury( it) chloride with TeBr, gives the organyltellurium tribromides RTeBr, and R' TeBr,, which may be reduced to the organyltellurium bromides RTeBr and R'TeBr, some metathesis reactions of which are described; or, in the presence of excess hydrazine, to diorganyl ditellurides, R, Te, and R' ,Te,. Reduction of RTeBr,X with NaBH, gave a novel tritelluride, R, Te, ; a method of preparation for R' ,Te, was also devised. Syntheses of the tellurides R,Te, R' ,Te, and RTe(C,H,OEt-p) were developed and the intermediacy of ionic compounds [ R,TeBr] [HgCIBr,] and [ R,TeCI] [HgCI,] noted. The crystal structures of 2-(2-pyridyl)phenyltellurium(iv) tribromide, (1 ), dimethyldithiocarbamato [2-(2-pyridyl) phenyl] tellurium ( II), (2), and p-ethoxyphenyl2-(2-pyridy1)phenyltelluride, (3), have been determined from three-dimensional X-ray counter data. Complex (1 ) is triclinic, space group PT with a = 6.953(6), b = 8.382(1), c = 12.133(2) A, cx = 78.68(1), p = 82.87(4), y = 87.14(4)", and Z = 2; R = 0.0735 for 1 963 observed reflections. The co-ordination about Te is octahedral with a vacant equatorial position, two Br atoms apical, the third Brand the organic group equatorial [Te-C, 2.1 lO(19); Te-N, 2.244(14) A]. The compound is essentially monomeric, with a weak association between Te and Br [3.596(3) A] in a neighbouring molecule. Complex (2) is triclinic, space group Pf with a = 8.809(3), b = 9.032(5), c = 10.727(4) A, u = 83.06(4), p = 86.49(3), y = 63.68(4), and Z = 2; R = 0.041 7 for 2 502 observed reflections. The co-ordination about Te is trigonal bipyramidal, C ( l ) and two lone pairs of Te comprising the equatorial co-ordination and the S ( l ) atom together with the pyridyl-N atom axial [Te-C, 2.1 1 l ( 5 ) ; Te-N, 2.354(4) A]. No significant intermolecular contacts occur. Complex (3) is monoclinic, space group P2,lc with a = 13.422(2), b = 16.469(3), c = 7.71 l ( 3 ) A, B = 91.01 (2)", and Z = 4; R = 0.041 5 for 2 01 4 observed reflections. The Te atom is bonded to two C atoms. The N atom of the pyridyl ring is twisted away from Te [Te-N, 2.695(4) A] by rotation of the pyridyl ring about the pyridyl-phenyl bond by 23.2(3)", a manifestation of the trans effect of the TeC(ethoxypheny1) covalent bond.

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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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Lewis acid and Lewis base behaviour of a tellurium(II) compound: a mercury(II) complex of a bis-telluride ligand with a 13-member macrocyclic chelate ring

Cited by 41 publications

References 0 publications

Structural characterization of rare intramolecularly (1,4-Te⋯N) bonded diorganotellurides and their monomeric complexes with mercury(II) halides: Metal assisted C–H⋯X (Hg) interactions leading to supramolecular architecture

Structural characterization of rare intramolecularly (1,4-Te⋯N) bonded diorganotellurides and their monomeric complexes with mercury(II) halides: Metal assisted C–H⋯X (Hg) interactions leading to supramolecular architecture

Intramolecularly Coordinated 2‐Iminomethylphenyltellurium Compounds

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