Organoantimony(<scp>iii</scp>) compounds containing (imino)aryl ligands of the type 2-(RNCH)C6H4(R = 2′,4′,6′-Me3C6H2, 2′,6′-iPr2C6H3): bromides and chalcogenides

Preda, Ana Maria; Raţ, Ciprian I.; Silvestru, Cristian; Breunig, H. J.; Lang, Heinrich; Rüffer, Tobias; Mehring, M.

doi:10.1039/c2dt32494f

Cited by 22 publications

(21 citation statements)

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“…This lengthy route is probably the reason why 2‐iminomethylphenyltellurium species ( VI ) are less frequently described in the literature than other intramolecularly coordinated tellurium compounds ( I – V ) that are more readily available. Recently, 2‐iminomethylphenyl‐supported compounds of group 13, group 14, group 15, and the lighter group 16 elements, were prepared by the ortho ‐directed lithiation route, which prompted us to develop similar synthetic protocols also for tellurium species containing 2‐( tert ‐butyliminomethyl)phenyl‐ and 2‐(2′,6′‐diisopropylphenyliminomethyl)phenyltellurium species ( VI , Scheme ). Five archetypal tellurium compounds were prepared and fully characterized by heteronuclear NMR spectroscopy and X‐ray crystallography.…”

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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Section: Introductionmentioning

confidence: 99%

Intramolecularly Coordinated 2‐Iminomethylphenyltellurium Compounds

et al. 2017

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“…The organic bromide (E)-2-(2′,6′-i Pr 2 C 6 H 3 N=CH)C 6 H 4 Br was obtained using a procedure already described. 17 The 1 H, 13 C, 19 F and 119 Sn NMR spectra as well as 2D NMR spectra were recorded at room temperature on a VARIAN GEMINI 300S instrument, using solutions in CDCl 3 . The 1 H chemical shifts are reported in δ units (ppm) relative to the residual peak of the deuterated solvent (CHCl 3 , 7.26 ppm).…”

Section: Methodsmentioning

confidence: 99%

Hypercoordinated organotin(IV) compounds containing (imino)aryl ligands - [(E)-2-(2′,6′-iPr2C6H3N=CH)C6H4]SnR2X (R = Me; X = Cl, I; R = nBu, X = Cl, F, Br). Molecular structures and supramolecular aspects

Comşa¹,

Varga²,

Soran³

et al. 2020

Rev.Roum.Chim.

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Five new dialkyl(iminoaryl)tin(IV) halides, [(E)-2-(2′,6′i Pr 2 C 6 H 3 N=CH)C 6 H 4 ]SnR 2 X [R = Me, X = Cl (1), I (2); R = n Bu, X = Cl (3), F (4), Br (5)], were prepared by reacting either [(E)-2-(2′,6′-i Pr 2 C 6 H 3 N=CH)C 6 H 4 ]MgBr with R 2 SnCl 2 for 1 and 3, or by halogen exchange reaction between the chlorides [(E)-2-(2′,6′-i Pr 2 C 6 H 3 N=CH)C 6 H 4 ]SnR 2 Cl with KX (X = I, F, Br) for 2, 4 and 5, respectively. The compounds were characterized by solution multinuclear (1 H, 13 C, 119 Sn) NMR spectroscopy and mass spectrometry. The crystal and molecular structure of all five compounds was established by single-crystal X-ray diffraction. The NMR data for 1-5 are consistent with the presence of an intramolecular N→Sn coordination which results in a trigonal bipyramidal (C,N)SnC 2 X core, similar with that observed in solid state. In the crystal of 1-5 different supramolecular architectures, based on intermolecular X•••H and C-H•••π (Ar centroid) interactions, were evidenced and discussed.

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“…[10] Generally, an (imino)arylmetal moiety, [2-(RN=CRЈ)C 6 H 4 ]M (R, RЈ = H, alkyl, aryl), can be built following two different procedures: (1) Reaction of the corresponding organolithium [8b,10,11] or Grignard [12] reagents with metal halides. (2) Condensation reaction between an organometallic species containing a [2-(O=CRЈ)C 6 H 4 ]M group and an organic amine in an organic solvent.…”

Section: Introductionmentioning

confidence: 99%

Structural Diversity of Coordination Cores in Homoleptic Tetraaryltin(IV) Dioxolane, Aldehyde and Imines: The First Octacoordinated Double Helicate Tetraorganotin(IV) Compound

2013

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Reaction of [2‐{(CH2O)2CH}C6H4]Li with SnCl4 in a 4:1 molar ratio afforded [2‐{(CH2O)2CH}C6H4]4Sn (1), which was deprotected to give [2‐(O=CH)C6H4]4Sn (2). Homoleptic [2‐(RN=CH)C6H4]4Sn [R = Me2NCH2CH2 (3), 2,4,6‐Me3C6H2 (4), PhCH2 (5)] were obtained by condensation of 2 with the corresponding amine either in solution or by using a green, solvent‐free procedure for (imino)arylmetal species. All compounds were characterised by multinuclear NMR spectroscopy and mass spectrometry, and their molecular structures were determined by single‐crystal X‐ray diffraction. In all cases, the C4Sn core is distorted tetrahedral as a result of the combined effects of the intramolecular coordination of the heteroatoms from the organic ligands and the steric impediments imposed by the ligands. The overall coordination around tin was found to be different, that is, coordination numbers from six for 1 and 4, to seven for 3 and 5 and eight for 2. Compound 2 is the first example of a mononuclear tetraorganotin(IV) compound that contains an octacoordinated metal centre with a double helicate topology in the solid state. Multinuclear NMR spectroscopy studies in solutions of CDCl3 are consistent with equivalent organic groups attached to a tetracoordinate tin atom.

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Organoantimony(iii) compounds containing (imino)aryl ligands of the type 2-(RNCH)C₆H₄(R = 2′,4′,6′-Me₃C₆H₂, 2′,6′-ⁱPr₂C₆H₃): bromides and chalcogenides

Cited by 22 publications

References 55 publications

Intramolecularly Coordinated 2‐Iminomethylphenyltellurium Compounds

Intramolecularly Coordinated 2‐Iminomethylphenyltellurium Compounds

Hypercoordinated organotin(IV) compounds containing (imino)aryl ligands - [(E)-2-(2′,6′-iPr2C6H3N=CH)C6H4]SnR2X (R = Me; X = Cl, I; R = nBu, X = Cl, F, Br). Molecular structures and supramolecular aspects

Structural Diversity of Coordination Cores in Homoleptic Tetraaryltin(IV) Dioxolane, Aldehyde and Imines: The First Octacoordinated Double Helicate Tetraorganotin(IV) Compound

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Organoantimony(iii) compounds containing (imino)aryl ligands of the type 2-(RNCH)C6H4(R = 2′,4′,6′-Me3C6H2, 2′,6′-iPr2C6H3): bromides and chalcogenides

Cited by 22 publications

References 55 publications

Intramolecularly Coordinated 2‐Iminomethylphenyltellurium Compounds

Intramolecularly Coordinated 2‐Iminomethylphenyltellurium Compounds

Hypercoordinated organotin(IV) compounds containing (imino)aryl ligands - [(E)-2-(2′,6′-iPr2C6H3N=CH)C6H4]SnR2X (R = Me; X = Cl, I; R = nBu, X = Cl, F, Br). Molecular structures and supramolecular aspects

Structural Diversity of Coordination Cores in Homoleptic Tetraaryltin(IV) Dioxolane, Aldehyde and Imines: The First Octacoordinated Double Helicate Tetraorganotin(IV) Compound

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Organoantimony(iii) compounds containing (imino)aryl ligands of the type 2-(RNCH)C₆H₄(R = 2′,4′,6′-Me₃C₆H₂, 2′,6′-ⁱPr₂C₆H₃): bromides and chalcogenides