Seven-membered heterocycles. IV. 5-Hydroxy-2-chloro-4,5-dihydro-1-benzothiepin system

Traynelis, Vincent J.; Borgnaes, Dan M.

doi:10.1021/jo00797a013

Cited by 17 publications

(19 citation statements)

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“…Munguia et al Bond angles (°) C(9)-E-C(1) 104.57 (12) 104.84(18) 112.6(4) 109.9(4) 103.35(18) C(9)-E-C (15) 110.07 (12) 110.17 (17) for 1 to 104.84°for 2 with corresponding increases in C1-E-C15. As we would expect for compounds with no E-S interactions, the third angle (C9-E-C15) would also be close to 109.5°.…”

Section: Nrc Canadamentioning

confidence: 99%

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Lewis acidity of group 14 elements toward intramolecular sulfur in ortho-aryl-thioanisoles

Munguia¹,

Pavel²,

Kapoor³

et al. 2003

Can. J. Chem.

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The series of compounds (o-CH 3 SC 6 H 4 )CH 2 EPh 3 (E = Si (1), Ge (2), Sn (3), and Pb (4)) have been synthesized and characterized by NMR spectroscopy and by single crystal X-ray diffraction. Compounds 1 and 2 are isostructural with a triclinic crystal system and P-1 space group; however, morphotropic steps occur between Ge and Sn, and Sn and Pb. While the E-S distances in 1 and 2 are 3.985 and 3.974 Å, respectively,~100% of the sum of the respective van der Waals (vdW) radii, there is a notable distortion from tetrahedral geometry about E. Compound 3 is also triclinic with P-1 symmetry, but has two molecules in the unit cell that demonstrate a distorted tetrahedral geometry and intramolecular Sn-S distances of 3.699 and 3.829 Å, 88% and 91% of the sum of the vdW radii. Compound 4 has a Pb-S distance of 3.953 Å (91% of Σ vdW radii). The structure of the Grignard coupling product [o-(SCH 3 )C 6 H 4 CH 2 ] 2 is also reported.Résumé : On a réalisé la synthèse d'une série de composés de formule (o-CH 3 SC 6 H 4 )CH 2 EPh 3 dans lesquels E = Si (1), Ge (2), Sn (3) et Pb (4) et on les a caractérisés par spectroscopie RMN et par diffraction des rayons X par un cristal unique. Les composés 1 et 2 sont isostructuraux avec un système cristallin triclinique et un groupe d'espace P-1; toutefois, on notre des différences morphotropes entre le Ge et le Sn ainsi qu'entre le Sn et le Pb. Alors que les distances E-S dans les composés 1 et 2 sont respectivement de 3,985 et 3,974 Å, environ 100 % de la somme des rayons respectifs de van der Waals, on note une distorsion notable par rapport à la géométrie tétraédrique autour de E. Le composé 3 est aussi triclinique avec une symétrie P-1, mais la maille cristalline comporte deux molécules ce qui dé-montre la présence d'une géométrie tétraédrique déformée alors que les distances intramoléculaires Sn-S de 3,699 et 3,829 Å correspondent respectivement à 88 % et 91 % de la somme des rayons de van der Waals. Dans le composé 4, la distance Pb-S est de 3,593 Å (91 % de la somme des rayons de van der Waals). On a aussi déterminé la structure du produit de couplage de Grignard [o-(SCH 3 )C 6 H 4 CH 2 ] 2 .

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Section: Nrc Canadamentioning

confidence: 99%

“…Syntheses of o-(methylthio)benzoic acid (10), o-(methylthio)benzyl alcohol (10,11), and o-(methylthio)benzyl chloride (12) The syntheses of the group 14 derivatives of o-(methylthio)benzyl chloride were accomplished as illustrated below for the silicon derivative in similar yields.…”

Section: General Techniquesmentioning

confidence: 99%

Lewis acidity of group 14 elements toward intramolecular sulfur in ortho-aryl-thioanisoles

Munguia¹,

Pavel²,

Kapoor³

et al. 2003

Can. J. Chem.

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“…Reagent grade tetrahydrofuran (THF) was dried and distilled under nitrogen from a sodium benzophenone ketyl solution; toluene, benzene and hexane were dried and distilled from Na ribbon; pyridine was dried and distilled from NaOH. Diphenyltindichloride was purchased from Gelest; 2-methoxybenzyl chloride, 2-ethylbenzyl alcohol, thionyl chloride, metallic tin, 1M tin tetrachloride in methylene chloride, 1-bromo-3-chloropropane, methanethiol and 1M HCl in diethyl ether were purchased from Aldrich; 2-thiomethylbenzyl chloride was synthesized by published methods 5. NMR spectra, 1 H, 13 C and 119 Sn, were recorded on a Bruker 300 MHz operating spectrometer at 300.00, 75.422 and 111.853 MHz, respectively, using CDCl 3 or C 6 D 6 as solvent.…”

Section: Methodsmentioning

confidence: 99%

Intramolecular Chalcogen−Tin Interactions in [(o-MeEC₆H₄)CH₂]₂SnPh_2−nCl_n (E = S, O, CH₂; n = 0, 1, 2) and Intermolecular Chlorine−Tin Interactions in the meta- and para-Methoxy Isomers

et al. 2010

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Organotin(IV) compounds of the type [(o-MeE-C 6 H 4 )CH 2 ] 2 SnPh 2-n Cl n were synthesized, E = O, n = 0 (1), n = 1 (2), n = 2 (3), E = S, n = 0 (4), n = 1 (5), n = 2 (6) and E = CH 2 , n = 0 (7), n = 1 (8), n = 2 (9). The dichloro compounds 3 and 6 have been investigated by single crystal X-ray diffraction and exhibit bi-capped tetrahedral geometry at the tin atom as a consequence of significant intramolecular Sn⋯O (3) and Sn⋯S (6) secondary bonding, in monomolecular units. Compound 3 when crystallized from a hexane/thf solvent mixture shows two different conformers, 3′ and 3″, in the crystal structure, 3′ has two equivalent Sn⋯O interactions, while 3″ has two non-equivalent Sn⋯O interactions. Upon recrystallization of 3 from hexane only a single structural form is observed, 3′. The Sn⋯E distances in 3′, 3″, and 6 are 71.3; 73.5, 72.9; and 76.3% of the ΣvdW radii, respectively. The meta and para-substituted isomers of 3 (10, 11) exhibit a distortion at the tin atom due to self-association via intermolecular Sn⋯Cl interactions resulting in polymeric structures. 119 Sn NMR spectroscopy suggests that the intramolecular Sn⋯E interactions persist in solution for the dichloride compounds 3 and 6.

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“…(R = n-Pr, Ph) were synthesized using the methods reported in the literature. [103][104][105] It is well established that Group 14 elements have the ability to expand their coordination number through dative interactions of Lewis bases of functional groups containing N, P, S and O donor atom). 95 This strategy was used to produce a variety of hypercoordinated compounds of Sn.…”

Section: Synthesismentioning

confidence: 99%

“…99 Dative interaction between Sn-P can be inferred from the upfield shifts of 119 Sn NMR resonance signals and short Sn-P distances and the large values of the J119Sn-31P coupling constant compared to tetracoordinated tin compounds. 102,103 The ligands used to obtain the molecules having Sn-P interaction are given in Figure 24. )2SnPhCl 179a which showed 119 Sn resonance of -126.4 ppm.…”

Section: Cp-chelating Ligand Containing Compounds Of Group 14mentioning

confidence: 99%

The preparation and characterization of structurally stable 5-coordinate polystannanes

Khan¹

2021

Preprint

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Tetraorganotin compounds [2-(MeOCH2)C6H4]SnR3 (R = Me, n-Bu, Ph) containing a C,O-chelating ligand were prepared in good yield from the reaction of the R3SnCl and [2-(MeOCH2)C6H4]Li. Tethered organotin compounds Ph3Sn(CH2)3OC6H4R (R = Ph, H, CF3, OCH3) were prepared in good yield from the hydrostannylation reactions of the corresponding vinyl ethers with Ph3SnH. Conversion of two organotin compounds to triorganotin chlorides and diorganotin chlorides, (Ph3-nClnSn(CH2)3OC6H4R; R = H, Ph: n = 1, 2), was successfully carried out and characterisation afforded by NMR spectroscopy. X-ray crystallographic studies revealed a tetrahedral geometry for the tetraorganotin Ph3Sn(CH2)3OC6H4CF3, while five-coordinate trigonal bipyramidal structures with relatively short Sn-O (2.7-2.8 Å) interactions were observed for both mono- (Ph2ClSn(CH2)3OC6H4R; R = H, Ph) and dichloride (PhCl2Sn(CH2)3OC6H4R; R = H, Ph) species. Penta-coordinate diorganotin dichlorides containing a C,N- chelating ligand[2-(Me2NCH2)C6H4]RSnCl2 (R = Me, n-Bu, Ph) or C,O- chelating ligand [2-(MeOCH2)C6H4]RSnCl2 (R = Me, n-Bu, Ph) were prepared by treating RSnCl3 with the lithiated salts [2-(Me2NCH2)C6H4]Li and [2-(MeOCH2)C6H4]Li respectively. Organotin chlorides were successfully reduced with LiAlH4 or NaBH4 to produce novel hydrides. Catalytic dehydrocoupling of diorganotin dihydrides to yield polystannanes was explored using a variety of dehydrocoupling catalysts such as Wilkinson’s catalyst, Cp2ZrMe2 or TMEDA. In almost every instance this resulted in the formation of yellow coloured gummy polymeric materials of moderate molecular weights (Mw = 1 × 104 - 1 × 105 Da) and PDI’s (1.3-2.0). The stability of polystannanes containing tethered O or C,N- or C,O-chelating ligands was investigated in both solid and in solution using NMR and UV-Vis spectroscopies. These studies revealed an enhanced stability to ambient light in the solid state and in solution in the dark when compared to known poly(dialkyl)stannanes.

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Seven-membered heterocycles. IV. 5-Hydroxy-2-chloro-4,5-dihydro-1-benzothiepin system

Cited by 17 publications

References 0 publications

Lewis acidity of group 14 elements toward intramolecular sulfur in ortho-aryl-thioanisoles

Lewis acidity of group 14 elements toward intramolecular sulfur in ortho-aryl-thioanisoles

Intramolecular Chalcogen−Tin Interactions in [(o-MeEC₆H₄)CH₂]₂SnPh_2−nCl_n (E = S, O, CH₂; n = 0, 1, 2) and Intermolecular Chlorine−Tin Interactions in the meta- and para-Methoxy Isomers

The preparation and characterization of structurally stable 5-coordinate polystannanes

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Seven-membered heterocycles. IV. 5-Hydroxy-2-chloro-4,5-dihydro-1-benzothiepin system

Cited by 17 publications

References 0 publications

Lewis acidity of group 14 elements toward intramolecular sulfur in ortho-aryl-thioanisoles

Lewis acidity of group 14 elements toward intramolecular sulfur in ortho-aryl-thioanisoles

Intramolecular Chalcogen−Tin Interactions in [(o-MeEC6H4)CH2]2SnPh2−nCln (E = S, O, CH2; n = 0, 1, 2) and Intermolecular Chlorine−Tin Interactions in the meta- and para-Methoxy Isomers

The preparation and characterization of structurally stable 5-coordinate polystannanes

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Intramolecular Chalcogen−Tin Interactions in [(o-MeEC₆H₄)CH₂]₂SnPh_2−nCl_n (E = S, O, CH₂; n = 0, 1, 2) and Intermolecular Chlorine−Tin Interactions in the meta- and para-Methoxy Isomers