Synthesis and spectroscopic studies of organotin compounds containing the SnS bond

doi:10.1016/0022-1902(81)80042-5

Journal of Inorganic and Nuclear Chemistry

Volume 43, Issue 6, 1981, Pages 1351-1359

https://doi.org/10.1016/0022-1902(81)80042-5 Get rights and content

Abstract

The preparation of a number of organotin(IV) compounds, containing SnS bonds, is described. Their ¹³C and ¹H NMR and IR spectra are presented. In cases where either SnS or SnN may be expected, Mössbauer spectra show two sets of peaks consistent with these possibilities.

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Citation Excerpt :
In particular, the 1H and 13C signals for the butyl groups are easily identified in these correlation spectra. Moreover, the assignment of the signals observed in the 1H and 13C NMR at δ = 2.88/2.95 and 27.4/27.2 ppm to the CH2-S group, is corroborated by the correlation observed in the HSQC NMR spectra of compounds 1/2, respectively, in good agreement with previously reported 13CNMR spectra for related compounds [9]. The introduction of the endocyclic lactone group produced a shift of these signals to δ = 3.47/2.99 and 28.1/22.6 ppm for compounds 3/4, respectively (see Figs. S3–S6 in the Supporting Information).
Four related stannadithiane compounds containing different endocyclic functional groups -including ether (1), diether (2), lactone (3), and spirolactone (4)- were prepared. The conformational landscape has been fully determined for the 8-membered representative (compound 1) resulting in a distorted crown form with the butyl chains adopting an extended conformation. The infrared and Raman spectra of stannadithiane species have been measured and interpreted, aided by quantum chemical calculations and potential energy surface analysis. Special attention has been devoted to the analysis of the vibrational features of the heterocyclic moieties. The characteristic ν_as(SnS) and ν_s(SnS) stretching modes of the SnS₂ endo-cyclic group were clearly observed in the Raman spectra at around 340 and 315 cm⁻¹, respectively. The exo-cyclic ν(SnC) stretching modes were found near 590 and 565 cm⁻¹ for the antisymmetric and symmetric motions, respectively. Thermal behavior for compounds 2–4 has been determined by thermogravimetric methods.
Synthesis and characterization of a new chloro-di-phenyltin(IV) complex with 2-mercapto-nicotinic acid: Study of its influence upon the catalytic oxidation of linoleic acid to hydroperoxylinoleic acid by the enzyme lipoxygenase
2006, Journal of Organometallic Chemistry
The complex [(C₆H₅)₂SnCl(HMNA)] (1) where H₂MNA is thioamide 2-mercapto-nicotinic acid has been synthesized by reacting a methanolic solution of di-chloro-di-phenyltin(IV) Ph₂SnCl₂ with an aqueous solution of 2-mercapto-nicotinic acid, containing twofold amount of potassium hydroxide. The Sn/ligand molar ratio is 2:1. The complex was characterized by elemental analysis, FT-IR and Mössbauer spectroscopic techniques. In addition the crystal structure of the molecule was determined by an X-ray diffraction at 293(2) K. C₁₈H₁₄ClNO₂SSn is monoclinic, space group P2₁/n, a = 15.089(3) Å, b = 15.846(3) Å, c = 16.691(3) Å, β = 105.57(3)°, Z = 8. The ligand coordinates to the metal center through the exocyclic sulfur and the heterocyclic nitrogen atoms, forming a four membered ring. The coordination sphere around the tin(IV) ion is completed with two carbon atoms from the two phenyl groups and one chlorine atom. The geometry around the tin atom can be described either as trigonal bipyramidal or tetragonal pyramidal. Finally, the influence of the complex [(C₆H₅)₂SnCl(HMNA)] (1) upon the catalytic peroxidation of linoleic acid to hydroperoxylinoleic acid by the enzyme lipoxygenase (LOX) was also kinetically and theoretically studied and the results compared with the ones of the corresponding binuclear complex [(C₆H₅)₃Sn(MNA)Sn(C₆H₅)₃ · (acetone)] (2) reported in the literature.
Synthesis, structural characterization and in vitro cytotoxicity of organotin(IV) derivatives of heterocyclic thioamides, 2-mercaptobenzothiazole, 5-chloro-2-mercaptobenzothiazole, 3-methyl-2-mercaptobenzothiazole and 2-mercaptonicotinic acid
2003, Journal of Inorganic Biochemistry
Five new organotin(IV) molecules with the heterocyclic thioamides; 2-mercaptobenzothiazole (Hmbzt), 5-chloro-2-mercaptobenzothiazole (Hcmbzt), 3-methyl-2-mercaptobenzothiazole (mmbzt) and 2-mercaptonicotinic acid (H₂mna) of formulae [(n-C₄H₉)₂Sn(mbzt)₂] (1), [(C₆H₅)₂Sn(mbzt)₂] (2), {(CH₃)₂Sn(cmbzt)₂]·1.7(H₂O)} (3), [(n-C₄H₉)₂SnCl₂(mmbzt)₂·(CH₂Cl₂)] (4) and {[(C₆H₅)₃Sn]₂(mna)·[(CH₃)₂CO]} (5) have been synthesized and characterized by elemental analysis, ¹H-, ¹³C-NMR, FT-IR and Mössbauer spectroscopic techniques. Crystal structures of molecules 1, 3 and 5 have been determined by X-ray diffraction at 173(1) K (1 and 5) and 293(2) K (3). Compound 1 C₂₂H₂₆N₂S₄Sn, is monoclinic, space group C2/c, a=44.018(2), b=8.8864(5), c=12.8633(7) Å, β=104.195(5)°, Z=8. Compound 3 is also monoclinic, space group P2₁/c and a=17.128(2) Å, b=17.919(2) Å, c=7.3580(10) Å, β=98.290(10)°, Z=4. In both molecules 1 and 3, two carbon atoms from aryl groups, two sulfur and two nitrogen atoms from thione ligands form a distorted octahedral geometry around tin(IV) with trans-C₂, cis-N₂, cis-S₂ configurations. Compound 5 C₄₅H₃₉NO₃SSn₂ is monoclinic, space group P2₁/n, a=9.1148(2) Å, b=29.2819(6), c=15.5556(4) Å, β=106.2851(9)°, Z=4. Complex 5 contains two [(C₆H₅)₃Sn(IV)] moieties linked by a double deprotonated 2-mercaptonicotinic acid (H₂mna). Both tin(IV) ions are five coordinated. This complex is the an example of a pentacoordinated Ph₃SnXY system with an axial-equatorial arrangement of the phenyl groups at Sn(1) atom. Compounds 1, 3 and 5 were tested for in vitro cytotoxicity against the cancer cell line of sarcoma cells (mesenchymal tissue) from the Wistar rat, polycyclic aromatic hydrocarbons (benzo[a]pyrene) carcinogenesis. Compound 5 exhibits strong cytotoxic activity, while complexes 1 and 3 show less cytotoxic activity.
Rationalization of the metal-ligand bonding in organotin(IV) complexes of anionic nitrogen heterocycles containing a thioketo exocyclic group. The case of 1-organyl-1H-tetrazole-5-thiones
1997, Polyhedron
A systematic crystallographic study of organotin(IV) complexes of the 1-phenyl-1H-tetrazole-5-thiolato heterocycle (L), has been undertaken in order to examine the metal-ligand bonding behaviour. The structural evidence accumulated from several X-ray determinations of complexes of the type SnR₃L and SnR₂L₂ performed mainly by us, as well as that of dimethylbis(1-phenyl-1H-tetrazole-5-thiolate)tin(IV), SnMe₂L₂, presented in this manuscript (the first reported with a heterocyclic ligand containing the
unit and two non-bulky organic groups), has led to propose a rationalization of the solid-state bonding behaviour of organotin(IV) derivatives toward tetrazolethiolates and closely related ligands.
The in vitro trypanocidal activity of organotin compounds
1997, European Journal of Medicinal Chemistry
A series of alkyl (aryl) thio organotin compounds were synthesized as potential trypanocidal drugs. These derivatives were prepared by the treatment of alkyl (or aryl) tin chlorides or oxides with thiols. Compounds were evaluated for trypanocidal activity using in vitro cultures of Trypanosoma equiperdum. Their efficiency for killing the parasites appeared to be under control of both the alkyl (or aryl) part of the molecule and the thio moiety. Several of the synthesized compounds exhibited a high in vitro levels of activity compared with the arsenic derivatives used for chemotherapy.
Complexes of dibutyldihalotin(IV) with imidazole and pyrazole. The crystal structure of dibutyldichlorobis(pyrazole)tin(IV)
1992, Journal of Organometallic Chemistry
Complexes of the type [SnBu₂X₂L₂] (X=Cl or Br; L=HIm or HPz) were obtained from the reaction of SnBu₂X₂ with imidazole (HIm) or pyrazole (HPz). The structure of dibutyldichlorobis (pyrazole)tin(IV) was determined by X-ray diffraction. The crystal consists of discrete all-trans SnBu₂Cl₂(HPz)₂ units with the metal atom octahedrally coordinated to two butyl carbons, two Cl atoms and two pyrazole rings. The pyrazole ligands are bound intra- and inter-molecularly to the chlorine atoms. IR data suggest similar trans-stereochemistry for the other compounds prepared. The ¹³C NMR spectra indicate that [SnBu₂X₂(HPz)₂] dissociates completely in DMSO-d₆ but only partially in CDCl₃.

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^†: Present address: Department of Chemistry, University of British Columbia, Vancouver, B.C., Canada V6T 1W5.

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Synthesis and spectroscopic studies of organotin compounds containing the SnS bond

Abstract

Spectrochim. Acta

Adv. Inorg. Chem. Radiochem.

J. Organomet. Chem.

Inorg. Chim. Acta

J. Organomet. Chem.

J. Organomet. Chem.

J. Organomet. Chem.

J. Organomet. Chem.

Prog. Inorg. Chem.

Can. J. Chem.

Org. Magn. Resn.

Can. J. Chem.