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

Barbul, Ioana; Varga, Richard A.; Silvestru, Cristian

doi:10.1002/ejic.201300245

Cited by 14 publications

(18 citation statements)

References 66 publications

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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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“…1 -ORTEP representation at 30% probability and the atom numbering scheme for compound 1 (hydrogen atoms are removed for clarity). 2,19,20 The longer…”

Section: Condensation Reaction To Obtain Compoundmentioning

confidence: 99%

“…[1][2][3][4][5] These type of derivatives have been obtained, until recently, starting from a imine containing ligand either by ortho-lithiation of the ligand and subsequent reaction with tin derivatives [6][7][8] or orthometalation through rearrangement of benzylideneaminotin(IV) halides. 9,10 Derivatization of a carbonyl group from an organic moiety bonded to tin with different amines gives organotin(IV) compounds that can (i) stabilize unusual species, 1 (ii) coordinate to other metal centers through additional donor atoms or groups present in the parent amine 2,5 or (iii) result in homobimetallic derivatives by using diamines. 5 On the other hand, homobimetallic organotin(IV) compounds with C,N-pendant arm ligands can be obtained by using sulfur to bridge two tin atoms.…”

Section: Introduction *mentioning

confidence: 99%

“…[2-(1,1'-C 6 H 5 C 6 H 4 -4-N=CH)C 6 H 4 ]SnMe 2 Cl (1) was performed by mixing [2-(O=CH)C 6 H 4 ]SnMe 2 Cl 5 with (1,1'-biphenyl)-4-amine in the absence of a solvent or catalyst, as described previously for related organotin(IV) species. [1][2][3][4][5] Total conversion to the desired compound was confirmed by the 1 H NMR spectra of the crude product. Reaction of imine 1 with sodium sulfide gave the homobimetallic derivative 2.…”

Section: Introduction *mentioning

confidence: 99%

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Synthesis and characterization of novel homobimetallic organotin(IV) compounds

Someşan¹,

Barbul²,

Vieriu³

et al. 2020

Rev.Roum.Chim.

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The (imino)aryltin(IV) chloride [2-(1,1'-C 6 H 5 C 6 H 4-4-N=CH)C 6 H 4 ]SnMe 2 Cl (1) was prepared by mixing [2-(O=CH)C 6 H 4 ]SnMe 2 Cl with (1,1'-biphenyl)-4amine in the absence of a solvent or catalyst. Reaction of 1 with sodium sulfide gave [{2-(1,1'-C 6 H 5 C 6 H 4-4-N=CH)C 6 H 4 }SnMe 2 ] 2 S (2). Treatment of 2 with ZnCl 2 or ZnSO 4 led to the isolation of the corresponding chloride (1) or sulfate [{2-(1,1'-C 6 H 5 C 6 H 4-4-N=CH)C 6 H 4 }SnMe 2 ] 2 SO 4 (3), respectively. All compounds were characterized in solution by multinuclear (1 H, 13 C and 119 Sn) NMR spectroscopy and mass spectrometry. In solid state, for all derivatives, IR spectroscopy confirms the presence of C=N double bonds, while singlecrystal X-ray diffraction analyses revealed the presence of pentacoordinated metal centers with a distorted trigonal bipyramidal geometry.

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“…The interest for this C , O‐ chelating ligand increases recently owed to its ability to generate organometallic Schiff‐bases via facile condensation reactions with primary amines, [ 38a,b,f ] along with catalytic or biological properties found for some derivatives. [ 31,42 ]…”

Section: Introductionmentioning

confidence: 99%

C,O‐Chelated organotin(IV) derivatives as potential anticancer agents: Synthesis, characterization, and cytotoxic activity

Someşan

Vieriu

Crăciun

et al. 2022

Applied Organom Chemis

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Organotin(IV) chemistry is nowadays in a continuous expansion due to the biological and medicinal potential found for some of these species. Within this study, the cytotoxic activity of several organotin(IV) compounds was investigated on two lung cancer cell lines (H522 and SK‐MES‐1) and on a normal lung cell line in order to have an overview of the toxicity and the selectivity of these derivatives. Moreover, the synthetic protocols, as well as the structural particularities of the novel organotin(IV) species, are also discussed. Hydrolysis of [2‐{(CH2O)2CR}C6H4]2SnPh2 [R = H (1), Me (2)] with p‐toluenesulfonic acid as a proton source afford the expected derivatives [2‐(O═CR)C6H4]2SnPh2 [R = H (3), Me (4)]. When hydrochloric acid is used in these reactions, a chlorine‐phenyl exchange took place in addition to the removal of the acetal fragments and the following products [2‐(O═CR)C6H4]2SnPhCl [R = H (5), Me (6)] were isolated. Treatment of 5 with 2 equiv of 3‐aminomethylpyridine in neat affords the imino(aryl)tin compound 2‐(3′‐PyCH2N═CH)C6H4]2SnPhCl (7). The reaction between 6 and potassium nicotinate allows the isolation of the organotin(IV) carboxylate [2‐{O═C (CH3)}C6H4]2SnPh[O(O)CC5H4N‐3] (8). Compounds 1–8 were characterized by multinuclear NMR spectroscopy in solution, mass spectrometry, and IR spectroscopy, and their molecular structures were confirmed by X‐ray diffraction analysis. Compounds 1–8 were investigated for their antitumoral effects on Homo sapiens lung cancer cell lines (H522 and SK‐MES‐1) and on a normal bronchial epithelial cell line, BEAS‐2B.

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

Cited by 14 publications

References 66 publications

Intramolecularly Coordinated 2‐Iminomethylphenyltellurium Compounds

Intramolecularly Coordinated 2‐Iminomethylphenyltellurium Compounds

Synthesis and characterization of novel homobimetallic organotin(IV) compounds

C,O‐Chelated organotin(IV) derivatives as potential anticancer agents: Synthesis, characterization, and cytotoxic activity

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