Dialkyltin Dichloride Research Articles

New Schiff Base Derived Organotin (IV) Complexes: Synthesis, Characterization, In vitro and In silico Biological Studies

Aims: The creation and testing of new Schiff base-based antibacterial organotin (IV) complexes were the objectives of this investigation. Background: Due to developed resistance, antibiotics that were once often used to treat microor-ganisms are no longer effective against them. It is thought that organotin compounds synthesized from Schiff bases have significant pharmacological effectiveness and work well as antibacterial agents. Methods: Thiocarbohydrazide and dehydroacetic acid were condensed to create the Schiff base, followed by processing with dialkyltin(IV)dichloride to synthesize the final product. Modern an-alytical techniques were used to clarify the compounds' probable structural details. The crystalline nature of the produced compounds was tested using PXRD. Results: All of the compounds were thermally stable up to 300°C. All of the synthesized com-plexes showed potent antibacterial activity in the range of 250 to 400 μg/ml. Furthermore, the computational biology research showed that, in contrast to ligands, which had a binding energy of -7.3 to -7.4 kcal/mol, complexes interacted well with dihydropteroate synthase and DNA gy-rase. Conclusion: The current study offered a unique technique for synthesizing diorganotin(IV) de-rivatives of N-substituted Schiff bases that are physiologically active. The results show that the chemicals created are promising antibacterial mediators against diseases that affect humans in the modern world. It might also open the door to future studies on drug-resistant microorganisms that could have biological uses.

Simulated gastric hydrolysis and developmental toxicity of dimethyltin bis(2-ethylhexylthioglycolate) in rats.

Dimethyltin dichloride is used as the putative toxophore for dimethyltin bis-alkylthio esters in a read-across approach. Recent chemical and toxicological investigations challenges this read across as data on dioctyltin bis(2-ethylhexyl thioglycolate) and dibutyltin bis(2-ethylhexyl thioglycolate) showed the dialkyltin thioglycolates do not generate dialkyltin dichloride. Results obtained by 119Sn-NMR spectroscopy demonstrated that dimethyltin bis(2-ethylhexyl thioglycolate), the smallest commercially manufactured dialkyltin thioester molecule of this kind, hydrolyzed to dimethyltin chloro-(2-ethylhexyl) thioglycolate under simulated gastric conditions. These studies did not detect dimethyltin dichloride. Dimethyltin bis(2-ethylhexyl thioglycolate) was administered orally to timed-pregnant Wistar-Han rats in an Arachis oil vehicle at 5, 10, and 25mg/kg/day [Gestation Day 6 (GD6) through GD20] with no maternal deaths observed. At 25mg/kg/day treatment statistically significant reductions occurred in feed consumption (-9%), maternal body weight (-2.4%) and adjusted maternal weight gain (-68%). There were no adverse gestational findings. Maternal thymus weight was significantly reduced in rats at 25mg/kg in the absence of changes in hormone levels of T3, T4 or TSH. There were no effects on fetal growth, no dose-dependent pattern of external, visceral, or skeletal malformations and no toxicologically relevant increase in anatomical variations at any dose group. Based on the obtained experimental data it is concluded that dimethyltin bis(2-ethylhexyl thioglycolate) forms dimethyltin chloro-(2-ethylhexyl thioglycolate), not dimethyltin dichloride, in the stomach environment at pH 1.2, and dimethyltin bis(2-ethylhexyl thioglycolate) was not teratogenic nor fetotoxic in rats. The maternal NOAEL was 10mg/kg/day, and the developmental NOAEL was 25mg/kg/day, the high dose. The maternal LOAEL was 25mg/kg/day based on decreased food consumption, lower adjusted mean body weight gain and reduced maternal thymus weight.

Supramolecular diorganotin(IV) complexes of N′-(2-hydroxynaphthalen-1-yl)methylene)formohydrazide: Synthesis, spectroscopic characterization, X-ray structure, antibacterial screening, cytotoxicity and docking study

Three organotin(IV) complexes [Me2SnL(1), Ph2SnL(2), tert-Bu2SnL(3)] have been synthesized by the reaction of a novel ligand N'-(2-hydroxynaphthalen-1-yl)methylene)formohydrazide (H2L) with dialkyltin(IV) dichlorides [R2SnCl2 (R = Me, Ph, tert-Bu) in presence of Et3N. The ligand and complexes have been characterized by elemental analysis, mass spectrometry, FT-IR, 1H, 13C and 119Sn NMR spectroscopic techniques. The spectroscopic data suggests coordination of ligand to the diorganotin(IV) moieties via oxygen nitrogen donor sites and five coordinated tin centers. The molecular structures of ligand (H2L) and complexes (1, 3) were also confirmed by single crystal X-ray analysis. The solid state structure of ligand showed it to be in the amido form whereas the single crystal X-ray analysis of complexes revealed the dibasic tridentate nature of ligand and monometallic nature of complexes. In both the complexes (1, 3) the Sn atom is in a distorted five-coordinate square pyramidal geometry with trigonality index(τ) 0.33 and 0.41, respectively. Packing diagrams reveal the important role of H…H, CH…π and O…H interactions in generating the supramolecular assembly. The antibacterial potential of all the compounds was investigated against two gram-positive bacteria (Bacillus subtilis, Stephlococcus aureus) and four gram-negative bacterial strains (Escherichia coli, Shigella flexenari, Pseudomonas aeruginosa, Salmonella typhi), using imipenem as the standard drug. Complex 2 exhibited highest activity against Bacillus subtilis and highest cytotoxicity against brine shrimp nauplii with LD50 1.01 μg/mL. Molecular Docking investigations revealed the best target protein, the positive impact of diphenyltin(IV) moiety on the compound-protein binding and the important role of hydrogen bonding, pi-pi and hydrophobic forces in such type of interaction.

Reconnaissance of the reactions of carbamodithiolate salts with dialkyltin dichloride

Reactions of carbamodithiolate salts viz., c-C3H5NH3+(L1)− and c-C6H11NH3+(L2)− (L1 = cyclopropylcarbamodithioate, L2 = cyclohexylcarbamodithioate) with R2SnCl2 (R = Me or n-Bu) were investigated in dichloromethane for the first time. A series of four diorganotin(IV) complexes of composition [Me2Sn(L1)Cl] (1), [Me2Sn(L1)2] (2), [Me2Sn(L2)2] (3) and [n-Bu2Sn(L2)2] (4) were isolated and characterized by spectroscopic methods. The structures of the two carbamodithiolate salts and the diorganotin(IV) compounds 1-4 were accomplished by X-ray crystallographic analysis revealing distorted square pyramid geometry for 1, but skewed trapezoidal bipyramids for 2-4. Influence of the carbamodithiolate moiety on the hydrogen-bond interactions and non-covalent contacts, as well as on the packing of the structures, is discussed. The 3D Hirshfeld surfaces were mapped and used to study the intermolecular interactions.

A new benzodiazepine molecule and its interactions with diorganotin(IV)chlorides

2-Methyl-2,4-di-thiophen-2′,2″-yl-2,3-dihydro-1H-benzo[b][1,4]diazepine (L) has been synthesized through condensation of phenylene-1,2-diamine and 2-acetylthiophene, and its reactions with dialkyltin(IV)dichlorides have been studied. Two salts formulated as (LH)[R2SnCl3] (R=Et, 1; R=Me, 2) have been isolated. L and 1 were structurally characterized. The conformation of the benzodiazepine L, changes in 1 due to H-bonds formation. [Et2SnCl3]- is one of the rare examples of five coordinated tin(IV) species and has distorted trigonal bipyramidal geometry. H-bonding interactions, in 1, lead to the formation of supramolecular helices.

Catalytic properties of cross‐linked polystyrene grafted diorganotins in a model transesterification and the ring‐opening polymerization of ε‐caprolactone

AbstractThe catalytic properties of cross‐linked polystyrene grafted diorganotins of the types [PH](1−t)[P(CH2)11Sn‐n‐BuCl2]t and [PH](1−t){[P(CH2)11Sn‐n‐BuCl]2O}t/2, in which [PH] represents the monomeric unit of the cross‐linked polystyrene matrix and t is the degree of functionalization, were compared. The grafted chlorodistannoxane catalyst was completely characterized by elemental analysis, IR and Raman, 119Sn high‐resolution magic angle spinning (hr‐MAS) NMR and 117Sn CP‐MAS NMR spectroscopy. In spite of the spatial constraints and the potential steric demand resulting from cross‐linking, the grafted C11 chlorodistannoxane exhibited the same dimeric ladder complex arrangement as its nongrafted n‐butyl analog in the solid state and in solution. Moreover, 119Sn hr‐MAS NMR and 117Sn CP‐MAS NMR spectroscopy appeared to be complementary techniques for the assessment of the tin(IV) functionality of the grafted tetraalkyldichlorodistannoxane. The catalytic activity of the compounds was assessed in a model reaction, the transesterification reaction of ethyl acetate and n‐octanol, as well as in the ring‐opening polymerization (ROP) of ε‐caprolactone. Residual tin trace analysis was performed on the acquired reaction products. Whereas tin contents of the order of 20 ppm were found in the reaction products of the transesterification, tin leaching values were overall higher for the ROP, being less unfavorable, however, for the distannoxane ( ± 70 ppm) than for the dialkyltin dichloride ( ± 290 ppm). Quantitative liquid 1H NMR was applied to assess the conversions in both reactions, but also to determine various molecular parameters of the synthesized poly‐caprolactones. Furthermore, size exclusion chromatography was used to determine their polydispersity index. It was also demonstrated that 1H and 119Sn hr‐MAS NMR enable the chemical integrity and recycling ability of the catalyst to be assessed. Copyright © 2007 John Wiley & Sons, Ltd.

Polystyrene‐Supported Organotin Dichloride as a Recyclable Catalyst in Lactone Ring‐Opening Polymerization: Assessment and Catalysis Monitoring by High‐Resolution Magic‐Angle‐Spinning NMR Spectroscopy

Dialkyltin dichloride grafted to a cross-linked polystyrene, with the formula [P-H]((1-t))[P-(CH2)nSnBuCl2]t (P=[CH2CH(pC6H4)], t=the degree of functionalization, and n=6 or 11), is investigated as a recyclable catalyst in the ring-opening polymerization (ROP) of epsilon-caprolactone (CL). It is demonstrated that high-resolution magic-angle-spinning (HR-MAS) NMR spectroscopy is an invaluable tool to characterize completely the supported catalyst. The 2D 1H-13C HSQC HR-MAS spectrum, in particular, allowed extensive assignment of the 1H and 13C resonances, as well as accurate measurement of the (n)J((1)H-(117/119)Sn) and (n)J((13)C-(117/119)Sn) coupling constants. 1H and 119Sn HR-MAS NMR spectroscopy is presented as a monitoring tool for catalytic processes based on organotin compounds, particularly for the investigation of the extent to which polymerization residues are observable in situ in the material pores and for the assessment of the chemical integrity and recycling conditions of the grafted catalyst. From polymerization experiments with CL, initiated by n-propanol and with [P-H]((1-t))[P-(CH2)nSnBuCl2]t of various compositions as the supported catalyst, it appears that a partial 'burst' of the polystyrene support occurs when the length of the alkyl spacer is limited to n=6, as a result of polymer chains growing within the pores of the support. However, extension of the length of the aliphatic polymethylene spacer from 6 to 11 carbon atoms preserves the support integrity and allows the production of catalyst-deprived poly(epsilon-caprolactone) (PCL) oligomers. A preliminary attempt to recycle the heterogeneous catalyst has shown that very good reproducibility can be obtained, in terms of both catalyst activity and molecular-weight parameters of the as-recovered PCL polyester chains.

Syntheses and Crystal Structures of Diorganotin Derivatives of 2,5‐Dimercapto‐1,3,4‐thiadiazole

AbstractTwo novel trinuclear tin oxo clusters [(C2S3N2)R6Sn3O(OH)Y]·L [R = CH3, Y = OH, L = 1·5H2O (1); R = PhCH2, Y = OEt, L = 0 (2)], a pentanuclear tin macrocycle [(CH3)2Sn(C2N2S3)]5·CH2Cl2·3H2O (3) and [(PhCH2)4Cl2Sn(C2S3N2)] (4) have been synthesized by the reaction of 2,5‐dimercapto‐1,3,4‐thiadiazole with dialkyltin dichloride in ethanol (95%) or dichloromethane. Complexes 1−4 have been characterized by elemental analysis and IR, 1H, 13C and 119Sn NMR spectroscopy. The structures of 1−3 have been determined by X‐ray crystallography. Complexes 1 and 2 display a unique tricyclic structure consisting of fused five‐membered Sn2ON2 and four‐membered Sn2O2 rings that form a planar N2Sn3O2 skeleton, with a distorted trigonal bipyramidal coordination at tin. Complex 3 is a pentanuclear 35‐membered tin macrocycle containing the crown thioether‐type ligand in which all five tin atoms bond to the sulfur and nitrogen atoms with distorted octahedral geometries. The structures of complexes 1 and 3 are stabilized by hydrogen bonds or intermolecular non‐bonding S···S interactions. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

Syntheses, characterizations, and crystal structures of organotin(IV) chloride complexes with 4,4′‐bipyridine

AbstractThe organotin(IV) chlorides RnSnCl4−n (n = 3, R = Ph, PhCH2, n−Bu; and n =2, R = n−Bu, Ph, PhCH2) react with 4,4′‐bipyridine (4′4‐bpy) to give [(Ph3SnCl)2(4,4′‐bpy)1.5(C6H6)0.5] (1), [(PhCH2)3‐ SnCl]2 (4,4′‐bpy) (2), [(n−Bu)3SnCl]2(4,4′‐bpy) (3), [(n−Bu)2SnCl2(4,4′‐bpy)] (4), [Ph2SnCl2(4,4′‐bpy)] (5), and [(PhCH2)2SnCl2(4,4′‐bpy)] (6). The new complexes have been characterized by elemental analyses, IR, 1H, 13C, 119Sn NMR spectroscopy. The structures of (1), (2), (4), and (6) have been determined by X‐ray crystallography. Crystal structures of (1) and (2) show that the coordination number of tin is five. In complex (1), two different molecules exist: one is a binuclear molecule bridged by 4,4′‐bpy and another is a mononuclear one, only one N of 4,4′‐bpy coordinate to tin. Complex (2) contains an infinite 1‐D polymeric binuclear chain by weak Sn…Cl intermolecular interactions with neighboring molecules. In the complexes (4) and (6), the tin is six‐coordinate, and the 4,4′‐bpy moieties bridge adjacent dialkyltin(IV)dichloride molecules to form a linear chain. © 2004 Wiley Periodicals, Inc. Heteroatom Chem 15:338–346, 2004; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20016

A Tin-119 NMR investigation of phosphine and phosphine oxide adducts of organotin chlorides

The stoichiometry and structure of phosphine and phosphine oxide adducts of Ph 3SnCl, R 2SnCl 2 (R=Et, Pr, Bu, t-Bu, and Ph), and RSnCl 3 (R=Bu and Ph) were studied with Sn-119 spectroscopy. The shift of the Sn-119 resonance to a lower frequency upon adduct formation, the multiplicity of the resonance, the variation of P-31-Sn-119 coupling with the nature of the substituent, and the change in structure of the peaks with concentration and temperature were all used to determine stoichiometry and structure. The organotin chloride adducts readily exchange with base or with other adducts. The diorganotin dichlorides form only 1:1 adducts with tributylphosphine (TBP), even at high base to acid ratios, but most form 1:2 adducts (as several geometric isomers) with phosphine oxides at mole ratios above 1:1. The lower dialkyltin dichlorides prefer to form 1:1 adducts (at 1:1 mole ratios) with TBP rather than tributylphosphine oxide (TBPO), whereas diphenyltin dichloride and di( t-butyl)tin dichloride prefer TBPO adduct formation. The reactions of the trihalides with TBP and TBPO are complicated by aryl transfer or displacement of chloride by base and consequent ion formation.

Platinum- and palladium-catalysed Kocheshkov redistribution of dialkyltin dichlorides or tetraalkyltins with tin tetrachloride

The Kocheshkov redistribution reaction of tetraalkyltin or dialkyltin dichlorides with tin tetrachloride is effectively catalysed by platinum(II) or palladium(II) phosphine complexes, yielding alkyltin trichlorides in high yield and with high selectivity.

Synthesis and evaluation of the in vivo trypanocidal activity of water soluble organotin compounds

Aseries of (3-(2-methoxy)ethoxypropyl)tin derivatives were synthesized as potential trypanocidal drugs. The series included an alkyltin trichloride, a dialkyltin dichloride and the corresponding dialkyltin oxide, and six dialkyltin dithio derivatives. Compounds were evaluated for trypanocidal activity using in vitro cultures of Trypanosoma equiperdum and mice infected with the same strain of parasite for in vivo tests. Two of the title derivatives, the bis (3-(2-methoxy)ethoxypropyl)tin dichloride 2 and the corresponding bis (3-(2-methoxy)ethoxypropyl)tin oxide 3, appeared to be water soluble reagents. Furthermore, they are the first examples of organotin compounds presenting interesting in vivo trypanocidal activity.

Organotin Transition Metal Complexes of 18-Membered Binuclear Hexaazamacrocycles: Synthesis and Characterization

Abstract The template condensation reaction of diethylenetriamine with glyoxal or biacetyl using dialkyltin(IV) dichloride and divalent transition metal ions resulted in the formation of a new series of hetero-binuclear hexaazamacrocyclic complexes R2SnMLX2 where L = L1, L2, L3, L4; R = CH3, C2H5, M = Cu(II), Ni(II) and Zn(II); × = Cl or NO3. The structure and bonding of these macrocyclic ligands have been studied by elemental analyses, IR, 1H NMR, EPR and electronic spectral studies, magnetic susceptibility and molar conductance data. The coordination geometry around the metal ions is octahedral in all complexes and each metal ion is coordinated to the imine nitrogen and the bridging nitrogen of the diethylenetriamine moiety.

Synthesis and characterization of adducts of dichlorosulphato bis(1,3-propylenediamine)metal(II) complexes with dialkyltin dichlorides

Adducts of dichlorosulphato bis(1,3-propylenediamine)-metal(II) complexes with dialkyltin dichlorides, [R2Sn(MeCN) 2]2[M(NH(CH2)3NH)2(SO3Cl)2] (M = Cr, Fe, Co, Ni or Cu; R = Me or n-Bu) have been prepared. The positive shift in the symmetric SO3 stretch and splitting of the doubly degenerate (E) modes in their i.r. spectra suggest a covalent linkage for the SO3Cl− group. The adducts are non-electrolytes; magnetic moments and ligand field data suggest that each SO3Cl− group is monodentate, generating an octahedral geometry around the metal ions, except for NiII where tetragonal distortion is observed.

Synthesis and characterization of organotin(IV) chlorosulphates, Li 2[R 2Sn(SO 3Cl) 4], Ba[R 2Sn(SO 3Cl) 4] and Sn[R 2Sn(SO 3Cl) 4] (R = CH 3, C 2H 5, C 3H 7, C 4H 9)

The cosolvolysis of dialkyltin dichloride, R 2SnCl 2 (R = CH 3, C 2H 5, C 3H 7, C 4H 9 with stoichiometric amounts of either LiCl, BaCl 2 or SnCl 2 in excess of chlorosulphuric acid resulted in the formation of compounds of the type Li 2(R 2Sn(SO 3Cl) 4], Ba [R 2Sn(SO 3Cl) 4] and Sn[R 2Sn(SO 3Cl) 4] (R = CH 3, C 2H 5, C 3H 7, CH 4H 9). The compounds are hygroscopic in nature but are stable under dry N 2. The positive shift in sym. SO 3 str·ν 1( A) and splitting of degenerate E modes in the IR spectra of the compounds suggest the covalent linkage of the SO 3Cl group to the dialkyltin moiety. The observed molar conductance values of these compounds in DMSO suggest that these are 1:1 and 1:2 electrolytes. The presence of the methyl, ethyl, propyl and butyl groups has been inferred by the appearance of resonance peaks at the appropriate position in the 1H NMR spectra. In all the compounds, the chlorosulphate group is expected to be bonded in a monodentate manner maintaining hexa coordination around the tin atom.

Thermal dehydrochlorination and stabilization of polyvinylchloride in solution: Part VIII. Dialkyltin carboxylates: substitution reaction

The behaviour of dialkyltin dilaurates and of various dialkyltin maleates in the thermal stabilization of polyvinyl chloride (PVC) in solution is studied through kinetic measurements of HCl evolution, formation of dialkyltin dichloride, UV analysis of the polyene sequences, FTIR analysis of the carbonyl groups grafted onto the PVC and of the formation of double bonds, and the changes in molecular weight by size exclusion chromatography. The substitution of the carboxylate groups is confirmed in all cases and is much more efficient in the case of the maleates than of the dilaurate. However, the substitution reaction occurs only in the earliest stages of the stabilization. On the other hand, attempts to trace intermediate monochlorotin derivatives by polarography methods or Mössbauer spectroscopy are not conclusive.

Gas chromatographic determination of airborne dialkyltin dichlorides as hydride derivatives

A sampling and analysis method for airborne dibutyltin and dioctyltin dichlorides was developed. The air samples were collected on glass-fibre filters. The chlorides were desorbed with n-hexane and converted into hydrides using sodium borohydride. The hydride derivatives were analysed by capillary gas chromatography with flame ionization detection (FID). The identity of dibutyltin and dioctyltin dihydrides in standard solutions was confirmed by gas chromatography—mass spectrometry (GC—MS) and GC—Fourier transform infrared spectrometry. The presence of tin compounds in the fumes released from heated PVC plastics (at 225°C) was shown by GC—MS. The detection limit of the method was 0.02 μg/ml (for tin), corresponding to a concentration of 0.0003 mg/m 3 in an air sample of 120 l. The sensitivity of the method was about 50 times better with FID compared with optimum electron-capture detection conditions. This method can also be applied to the determination of dimethyltin dichloride.

Crystal structure of dimethyltin dichloride—dibenzylsulfoxide

Dimethyltin dichloride—dibenzylsulfoxide,[(CH 3) 2SnCl 2 · OS(CH 2C 6H 5) 2], crystallizes in the orthorhombic P2 12 12 1 space group with a sub-structure of dimensions a 8.007(2), b 12.134(3), c 19.595(5) Å; Z = 4. A superstructure lattice with a 64.06(2) Å ( a × 8) could not be fully characterized. The geometry of the five-coordinated tin atom is cis-trigonal bipyramidal with the methyl groups equatorial [SnC 2.109(16), 2.128(15) Å; CSnC 136.4(9)°], and the sulfoxide [SnO 2.319(10) Å] and one chloride [SnCl 2.464(6) Å] apical [ClSnO 173.9(4)°]. The complex is an unusual example of a monomeric five-coordinate 1 : 1 adduct of a dialkyltin dichloride with a monodentate Lewis base.

Spectral and Biological Studies on Organotin(IV) Complexes of Heterocyclic Benzothiazolines

Abstract The monobasic bidentate benzothiazolines, which were produced by the reaction of 2-mercaptoaniline and the heterocyclic aldehydes e.g., 2-furaldehyde, 2-thiophenecarbaldehyde, 2-pyridinecarbaldehyde, and 3-indolecarbaldehyde, have reacted with dialkyltin dichloride to give colored compounds. These compounds were characterized on the basis of elemental analyses, molar conductance, molecular weight determination, electronic and infrared spectral studies. Multinuclear NMR(1H, 13C, and 119Sn) data suggest trigonal bipyramidal and octahedral geometries for the resulting Me2SnCl(\ {NS}) and Me2Sn(\ {NS})2 type complexes where \ {NS} indicates benzothiazoline ligand, respectively. The fungitoxicity of 2-(2-thienyl)benzothiazoline and its complexes has been evaluated on pathogenic fungi.

ChemInform Abstract: Diorganotin(IV) Complexes of Bis‐ and Tris‐pyrazolyl and Bis‐pyridyl Methanes and Pyridyl Pyrazoles.

AbstractThe distorted octahedral Sn(IV) complexes (I) are prepared by equimolar reaction of the N donor ligands with corresponding dialkyltin dichlorides in hexane.