Triphenyltin Derivatives Research Articles

Synthesis, calf-thymus DNA interaction with trimethyl-/triphenyl-tin(IV) derivatives of ɑ-lipoic acid and their mixed ligand complexes with N-donor (1,10-phenanthroline/2,2′-bipyridyl/benzimidazole)

The mixed ligand complexes of trimethyl-/triphenyl-tin(IV) derivatives of ɑ-lipoic acid (HLA), viz. R3Sn(LA) {R = Me (1), and Ph (2)}with 1,10-phenanthroline (phen), viz. [Me3Sn(LA).phen] (3), 2,2′-bipyridyl, viz. [Ph3Sn(LA).by] (4) and benzimidazole (bz), viz. [R3Sn(LA).bz] {R = Me (5), and Ph (6)} were synthesised and satisfactorily characterized by analytical and spectroscopic techniques, especially FT-IR, NMR (1H, 13C, and 119Sn NMR) spectroscopy and ESI-MS spectrometry. The ∠C-Sn-C bond angle calculated by optimization of their gas-phase geometry revealed that complexes (1) and (2) have distorted tetrahedral geometry and complexes (3) and (4) exhibited distorted octahedral geometry while complexes (5) and (6) exhibited trigonal bipyramidal environment around the tin, which agreed with the data obtained from NMR. Spectroscopic titrations (UV–visible absorption, fluorescence titration, and circular dichroism) were performed to ascertain the binding mode of the complex with calf thymus DNA (CT-DNA). The obtained values of Kb in the order of 105 M−1 suggested partial intercalative interactions of complexes with DNA grooves/base pairs. The complexes efficiently cleaved plasmid DNA (pBR322) into supercoiled (Form I), nicked/circular (From II), and linear structure (Form III). The fascinating biophysical data suggests the potential of these complexes as anticancer agents.

Triphenyltin(IV) Carboxylates with Exceptionally High Cytotoxicity against Different Breast Cancer Cell Lines.

Organotin(IV) carboxylates are a class of compounds explored as alternatives to platinum-containing chemotherapeutics due to propitious in vitro and in vivo results, and distinct mechanisms of action. In this study, triphenyltin(IV) derivatives of non-steroidal anti-inflammatory drugs (indomethacin (HIND) and flurbiprofen (HFBP)) are synthesized and characterized, namely [Ph3Sn(IND)] and [Ph3Sn(FBP)]. The crystal structure of [Ph3Sn(IND)] reveals penta-coordination of the central tin atom with almost perfect trigonal bipyramidal geometry with phenyl groups in the equatorial positions and two axially located oxygen atoms belonging to two distinct carboxylato (IND) ligands leading to formation of a coordination polymer with bridging carboxylato ligands. Employing MTT and CV probes, the antiproliferative effects of both organotin(IV) complexes, indomethacin, and flurbiprofen were evaluated on different breast carcinoma cells (BT-474, MDA-MB-468, MCF-7 and HCC1937). [Ph3Sn(IND)] and [Ph3Sn(FBP)], unlike the inactive ligand precursors, were found extremely active towards all examined cell lines, demonstrating IC50 concentrations in the range of 0.076-0.200 µM. Flow cytometry was employed to examine the mode of action showing that neither apoptotic nor autophagic mechanisms were triggered within the first 48 h of treatment. However, both tin(IV) complexes inhibited cell proliferation potentially related to the dramatic reduction in NO production, resulting from downregulation of nitric oxide synthase (iNOS) enzyme expression.

Synthesis, spectroscopy and biological studies of triphenyltin(IV) derivatives with carboxylated Schiff bases

Synthesis, spectroscopy and biological studies of triphenyltin(IV) derivatives with carboxylated Schiff bases

Design, synthesis and biological evaluation of organotin(IV) complexes of flumequine and cetirizine

Six new organotin(IV) derivatives [Me3SnL1] (1), [Bu3SnL1] (2), [Ph3SnL1] (3), [Me3SnL2] (4), [Bu3SnL2] (5) and [Ph3SnL2] (6) (where HL1 = = 9-fluoro-6,7-dihydro-5-methyl-1-oxo-1H,5H-pyrido[3,2,1-ij]quinoline-2-carboxylic acid (flumequine) and HL2 = 2-[2-[4-[(4-chlorophenyl)phenylmethyl]- -1-piperazinyl]ethoxy] acetic acid (cetirizine)) were synthesized and characterized by elemental analysis, FT-IR spectroscopy, multinuclear 1H-, 13C- and 119Sn-NMR, mass spectrometry and thermal analysis techniques. The obtained data reveal trigonal-bipyramidal geometry in case of complexes 1, 2, 4 and 5, and tetrahedral geometry for complexes 3 and 6 around the tin atom, whereas in complexes 3 and 6 the carboxylate ligand act as monodentate ligand through one of its oxygen atoms while it acts as bidentate ligand through two oxygen atoms for complexes 1, 2, 4 and 5. The antibacterial and antifungal efficacies of complexes 1?6 were assessed and the majority of the compounds showed good activities. The present research showed that the trimethyltin(IV) derivatives were particularly more effective than tributyltin(IV) and triphenyltin(IV) derivatives against all the bacterial and fungal strains. Antioxidant and DNA binding studies were also performed and promising results were obtained.

Triphenyltin derivatives of sulfanylcarboxylic esters

The reaction of 3-(aryl)-2-sulfanylpropenoic acids [H2xspa; x: p=3-phenyl-, f=3-(2-furyl)-, t=3-(2-thienyl)-] with methanol or ethanol gave the corresponding methyl (Hxspme) or ethyl (Hxspee) esters. The reaction of these esters (HL) with triphenyltin(IV) hydroxide gave compounds of the type [SnPh3L], which were isolated and characterized as solids by elemental analysis, IR spectroscopy and mass spectrometry and in solution by multinuclear (1H, 13C and 119Sn) NMR spectroscopy. The structures of [SnPh3(pspme)], [SnPh3(fspme)] and [SnPh3(fspee)] were determined by X-ray diffractometry and the antimicrobial activity against E. coli, S. aureus, B. subtilis, P. aeruginosa, Resistant P. aeruginosa (a strain resistant to ‘carbapenem’), and C. albicans was tested and the in vitro cytotoxic activity against the HeLa-229, A2780 and A2780cis cell lines was determined for all compounds.

Sn- and Ge- triorganometallics exert different cytotoxicity and modulation of migration in triple-negative breast cancer cell line MDA-MB-231

Among a variety of metal containing organic compounds, tin derivatives are enjoying an increasing interest and appear to be very promising as potential drug candidates. We studied eight organometallic derivatives, nuclear retinoid X receptor (RXR) ligands and two germanium containing derivates that do not serve as RXR ligands. Tributylgermanium chloride (TBGe) and triphenylgermanium chloride (TPGe) did not inhibit growth of human triple negative MDA-MB-231 breast cancer cells. On the other hand, the tributyltin derivatives were highly, the triphenyltin derivatives less cytotoxic, both groups with IC50 values of nanomolar range. All trialkyltin derivatives (tributyltin chloride, tributyltin bromide, tributyltin iodide, tributyltin hydride) and three triaryltin derivatives (triphenyltin chloride, triphenyltin hydride and triphenyltin hydroxide) caused caspase-3/7 dependent apoptosis. Those derivatives that showed no or weak cytotoxicity, TBGe, TPGe, and triphenyltin acetate, we found to reduce migration of tested triple negative breast cancer cells.

Synthesis, characterization and antimicrobial activity of triorganotin(IV) derivatives of some bioactive Schiff base ligands

Triorganotin(IV) complexes of the type Me3Sn[OC(R1):CH(CH3)C:NR2OH] and Ph3Sn[OC(R′):CH(CH3)C:NR″OH] (R′ = ─CH3, ─C6H5; R″ = ─(CH2)2─, ─(CH2)3─) have been synthesized by the reactions of trimethyl/phenyltin(IV) chloride with the sodium salt of corresponding Schiff base ligands in unimolar ratio in refluxing tetrahydrofuran. All these compounds have been characterized using elemental analyses and their probable structures have been proposed on the basis of infrared, 1H NMR, 13C NMR, 119Sn NMR and mass spectroscopic studies. In the trimethyltin(IV) derivatives the central tin atom is tetracoordinated, whereas in the analogous triphenyltin(IV)derivatives the central tin atom is pentacoordinated. All these ligands, metal precursors and corresponding triorganotin(IV) complexes have been screened for antimicrobial activities. A comparison of activities of the ligands and their corresponding triorganotin(IV) derivatives has been made. Attempts have also been made to relate the activity to the structure of these compounds.

Development and Characterization of a Human Reporter Cell Line for the Assessment of Thyroid Receptor Transcriptional Activity: A Case of Organotin Endocrine Disruptors.

We developed and characterized the human luciferase reporter cell line PZ-TR for the assessment of thyroid receptor (TR) transcriptional activity. Triiodothyronine (T3) induced luciferase activity in a dose-dependent manner, and the sensitivity of assay allowed for the detection of nanomolar T3 concentrations. The luciferase activity was induced by a maximum of (2.42 ± 0.14)-(2.73 ± 0.23)-fold after 24 h of exposure to 10 nM T3. We did not observe a nonspecific induction of luciferase activity by other steroid hormones and VDR ligands, with the exception of partial activation by retinoic acids. Cryopreservation of PZ-TR cells did not influence their functionality, responsivity to T3, or cell morphology, even after long-term cultivation. PZ-TR cells were used to evaluate the effects of organic tin compounds on TR. We found that the tributyltin and triphenyltin derivatives induced luciferase activity and that application of organotins in combination with T3 enhanced the effect of T3. These findings indicate that organic tin compounds have potential to interfere with TR-mediated regulation of gene expression and influence the physiological activity of thyroid hormones.

The Coordination Chemistry in the Antifungal Effect of Tin(IV)-Bis(Pyrimidin-2-Ylthio)Alkane Derivatives

High productivity of agriculture goods is closely associated with the use of fungicides to reduce losses caused by the fungal plant diseases. However, appearance of resistant population of pathogens to several commercial fungicides is a common phenomenon that requires control. There is, therefore, need for developing novel fungicide compounds that are environmentally safe with low toxicity to wild life and humans. In this study novel organotin(IV) derivatives of bis(pyrimidin-2-ylthio)methane (ptm), bis(pyrimidin-2-ylthio)ethane (pte) and bis(pyrimidin-2-ylthio)hexane (pth) were tested against phytopathogens to evaluate their activity as potential fungicides. The bis(pyrimidin-2-ylthio)alkanes were not active in contrast with the organotin(IV) derivatives. The 5-coordinate triphenyltin(IV) derivatives were the most active compounds in a wide range of concentration. This study shows that the microorganisms were susceptible to the acid character of the organotin(IV) precursors.

Synthetic, Structural, and Spectroscopic Studies of Sterically Crowded Tin–Chalcogen Acenaphthenes

A series of sterically encumbered peri-substituted acenaphthenes have been prepared containing chalcogen and tin moieties at the close 5,6-positions (Acenap[SnPh3][ER], Acenap = acenaphthene-5,6-diyl, ER = SPh (1), SePh (2), TePh (3), SEt (4); Acenap[SnPh2Cl][EPh], E = S (5), Se (6); Acenap[SnBu2Cl][ER], ER = SPh(7), SePh (8), SEt (9)). Two geminally bis(peri-substituted) derivatives ({Acenap[SPh2]}2SnX2, X = Cl (10), Ph (11)) have also been prepared, along with the bromo–sulfur derivative Acenap(Br)(SEt) (15). All 11 chalcogen–tin compounds align a Sn–CPh/Sn–Cl bond along the mean acenaphthene plane and position a chalcogen lone pair in close proximity to the electropositive tin center, promoting the formation of a weakly attractive intramolecular donor–acceptor E···Sn–CPh/E···Sn–Cl 3c-4e type interaction. The extent of E→Sn bonding was investigated by X-ray crystallography and solution-state NMR and was found to be more prevalent in triorganotin chlorides 5–9 in comparison with triphenyltin derivatives 1–4. The increased Lewis acidity of the tin center resulting from coordination of a highly electronegative chlorine atom was found to greatly enhance the lp(E)−σ*(Sn–Y) donor–acceptor 3c-4e type interaction, with substantially shorter E–Sn peri distances observed in the solid state for triorganotin chlorides 5–9 (∼75% ∑rvdW) and significant 1J(119Sn,77Se) spin–spin coupling constants (SSCCs) observed for 6 (163 Hz) and 8 (143 Hz) in comparison to that for the triphenyltin derivative 2 (68 Hz). Similar observations were observed for geminally bis(peri-substituted) derivatives 10 and 11.

Syntheses, spectral characterization, X-ray studies and in vitro cytotoxic activities of triorganotin(IV) derivatives of p-substituted N-methylbenzylaminedithiocarbamates

Two new organotin(IV) complexes of the type R3SnL, where (L=p-bromo-N-methylbenzylaminedithiocarbamate and p-fluoro-N-methylbenzylaminedithiocarbamate, and R=phenyl) have been synthesized in 1:1molar ratio with good yields and isolated as crystalline solids. The newly synthesized compounds gave fairly sharp melting points indicating that the compounds were pure. A systematic investigation of the derivatives were carried out both in solid and in solution and were suitably characterized by elemental analysis, FT-IR, 1H, 13C, 119Sn NMR spectroscopies. The dithiocarbamate ligands chelated to the tin metal monodentately using only one sulfur atom showing a pair of bands due to ν(CS) below 1000cm−1. This phenomenon was supported by the occurrence of new medium to weak absorptions in the region 411–545, in the spectra of complexes, assigned to ν(SnS) and ν(SnC). The crystal structures of the two triorganotin(IV) complexes have been determined by X-ray crystallography. Both the complexes crystallized in the monoclinic, P2(1)/n space group. The spectral investigations and single crystal X-ray diffraction data illustrate that the two dithiocarbamato ligands in the triphenyltin(IV) derivatives 1 and 2 are monodentate and the geometry at tin is best described as a distorted tetrahedron. The in vitro antiproliferative tests of these two derivatives on three human cell lines, leukemic lymphoblastoma Jurkat cells, lymphoblastoma K-562 cells, hepatoblastoma HepG2 cells and one mouse fibroblast cells L929 show dose-dependent decrease of cell proliferation in all cell lines.

Synthesis and structural elucidation of bioactive triorganotin(IV) derivatives of sodium deoxycholate

Trimethyl (1), tributyl (2), and triphenyl tin (3) derivatives of sodium (R)-4-((3R,5R,8R,9S,10S,12S,13R,14S,17R)-3,12-dihydroxy-10,13-dimethyl-hexadecahydro-1H-cyclopenta[a]phenanthren-17-yl)pentanoate (sodium deoxycholate) were synthesized by refluxing sodium deoxycholate with the corresponding triorganotin(IV) chloride in 1 : 1 M ratio. All the three compounds were characterized by elemental analysis, infrared spectroscopy, 1H, 13C, 119Sn NMR, and X-ray diffraction studies. From FT-IR spectra, Δν values proposed bridging or chelating behavior of the ligand. The three compounds gave a trigonal bipyramidal geometry in the solid state and tetrahedral geometry in solution. Single crystal of 1 showed polymeric trigonal bipyramidal geometry. Synthesized compounds obtained were screened for their antimicrobial and antitumor activities against A2780 cell line. Results revealed that only 2 showed significant antibacterial activity. However, all the three compounds exhibited promising antifungal and anticancer activities.

Aggregation of Hydrogen Bonded Dimeric Tri-Organotin Amino Substituted Pyrimidine-2-Thiolates

The synthesis of six tri-organotin compounds with 4-amino and 4,6-diaminopyrimidine-2-thiolate is described. The compounds have the general formula R3Sn(thiolate) where R = Me, Bu, or Ph. The compounds are investigated by a variety of spectroscopic techniques both in solution and in the solid state. The environment around the tin centres proves to be tetrahedral with monodentate thiolate anions as is inferred from the infrared and NMR spectra. The coordination sphere is not affected even by the presence of DMSO as solvent. In the solid state, the crystal structure determination of the trimethyl and triphenyltin derivatives of the 4,6-diaminopyrimidine-2-thiolate ligand, reveal an association into centrosymmetric dimers through N–H⋯N hydrogen-bonding interactions leaving the organotin site practically unaffected. However, in addition to the classical hydrogen bonding, weaker N–H⋯RS and N–H⋯Rπ interactions are also present and play an important role in determining further aggregation of these dimers which gives rise to a three-dimensional polymeric structure in the case of the trimethyltin and a layer of dimers in the case of the triphenyltin derivative, respectively.

Toxicity and speciation analysis of organotin compounds

The use of antifouling paints in shipbuilding has led to a significant concentration of organotin compounds in the marine environment. Antifouling paints have become the main source of tributyltin and triphenyltin derivatives loaded into the sea. The toxicity of organotin compounds has been of great concern. High concentrations of organotin compounds are associated with growth abnormalities in mussels and oysters and have also resulted to the decline in their abundance. High concentration of organotin compounds have also been found in the tissues of marine mammals and its presence has been linked to mass mortalities of marine mammals. It causes imposex and calcification anomalities in mollusks. Seafood is thought to be a possible source of organotin compounds in human. Therefore, to evaluate the environmental distribution and fate of these compounds and to determine the effectives of legal provisions adopted by a number of countries, a variety of analytical methods have been developed for the speciation of organotin compounds in the environment. A detailed review of the toxicity and chemical speciation of organotin compounds is given.

Synthesis and characterisation of organotin(IV) derivatives of ambidentate ligands containing nitrogen and sulphur donor atoms

Abstract A series of organotin(IV) derivatives of bis(pyrimidin-2-ylthio)methane (ptm), 1,2-bis(pyrimidin-2-ylthio)ethane (pte) and 1,6-bis(pyrimidin-2-ylthio)hexane (pth) have been prepared in dichloromethane at room temperature. The 2:1 (M/L) molar ratio compounds have a general formula of [Sn2ClxPh8-xL] (x=2, 4, 6, 8; L=ptm, pte and pth). A 1:1 complex was also obtained by reacting SnClPh3 with pth. The organotin derivatives were characterised by multinuclear NMR (1H, 13C and 119Sn) and infrared spectroscopy, gel permeation chromatography (GPC), microanalysis and melting point. In the triphenyltin derivatives, 1, 5, 9 and 10 the tin atoms show a distorted trigonal-bipyramidal configuration where the ligand is monodentate towards the metal atom. In the compounds 2–4, 6–8 and 11–13, the tin atoms each exhibit a distorted octahedral configuration. Chelation is formed between the tin nucleus and the coordinating sulphur and nitrogen atoms. The correlation between the 1J(13C-119Sn) and C-Sn-C bond angle indicates formation of 5-coordinate compounds.

Synthesis, Infrared and Mössbauer Studies of New Mono- Di- and Trinuclear Oxalato Triphenyltin (Iv) Derivatives

Article Synthesis, Infrared and Mössbauer Studies of New Mono- Di- and Trinuclear Oxalato Triphenyltin (Iv) Derivatives was published on October 1, 2010 in the journal Main Group Metal Chemistry (volume 33, issue 4-5).

Synthesis and Biological Activities of New Triphenyl Organotin (IV) Based on the Pyrazole Carboxylic Acids

The synthesis of new triphenyltin derivatives with (N-substituted-pyrazol-3-yl) carboxylic acid fragments is described. The in vitro antibacterial activity of the new agents was evaluated against two fungal strains (Saccharomyces cerevisiae and Fusarium oxysporum f.sp albedinis) and against bacterial strains (Echerichia coli). A considerable activity was recorded with respect to the three studied micro-organisms. Structure activity relationship studies (SAR) reflect the effect of substituted pyrazolic fragment.

Some Triarylgermyl Substituted Chiral Triphenyltin Derivatives: Their Synthesis, Characterisation and X-Ray Crystal Structure

Some chiral triphenyltin complexes (1-4) derived from triarylgermyl(substituted)-propenoic acids (I-D) have been prepared. They were characterized by IR, mass spectrometry and multinuclear (H-1, C-13, Sn-119) NMR spectroscopic techniques and their chirality was established on the basis of H-1 NMR data and specific rotation values. X-Ray structure of the synthesized ligand, I-D3, (m-CH3C6H4)(3)GeCH(C6H5)CH2COOH, depicts chiral and prochiral carbons explicitly and described tetrahedral geometry around the germanium atom.

New triorganotin(IV) derivatives of dipeptides as anti-inflammatory–antimicrobial agents

New triorganotin(IV) derivatives of dipeptides with general formulae R 3Sn(HL), where R = Me and/or n-Bu and/or Ph and HL is the monoanion of glycylglycine (H 2L-1), glycylvaline (H 2L-2), glycylleucine (H 2L-3), glycyltryptophane (H 2L-4) and glycyltyrosine (H 2L-5) have been synthesized and characterized on the basis of infrared, multinuclear NMR and 119Sn Mössbauer spectroscopic studies. All the newly synthesized compounds were examined for their in vivo anti-inflammatory activity (using the carrageenan-induced paw edema bioassay in rats), acute toxicity (LD 50) and cardiovascular activity. These compounds were also screened for their in vitro antimicrobial activity against Staphylococcus aureus Mau (29/58) and (78/71), Bacillus subtilis (18/64), Escherichia coli (326/71), Candida albicans (Pn-10), Microsporum gypseum and Euglena gracillis. The results revealed that triphenyltin(IV) derivatives exhibited anti-inflammatory activity comparable to that of phenylbutazone with high safety margin (LD 50 > 500 mg kg –1). Further Ph 3Sn(Gly-Val) displays a potent cardiovascular activity. Moreover, most of the compounds displayed appreciable antibacterial activities when compared with ampicillin and norfloxacin. Compounds Ph 3Sn(Gly-Gly) and Ph 3Sn(Gly-Val) are the most distinctive derivatives identified in the present study because of their promising in vivo anti-inflammatory activity and in vitro antibacterial activity against gram-positive and -negative bacteria.

Synthesis, spectroscopic studies and X‐ray crystal structures of triorganotin(IV) derivatives containing 3,5‐dinitrobenzoate, N‐methylanthranilate and dicyclohexylacetate ligands

AbstractThe synthesis and spectroscopic characterization (infrared, 1H, 13C, 119Sn NMR and 119Sn Mössbauer) of three organotin derivatives incorporating carboxylate ligands, with general formulae (C6H11)2CHCOOSnPh3 (1), (CH3NH)C6H4COOSnPh3 (2) and 3,5‐(NO2)2C6H4CO2SnMe3 (3) are reported together with their X‐ray crystal structures. The compounds were obtained by the condensation, in ethanol, of the appropriate carboxylic acid with triphenyltin hydroxyde (1, 2) or trimethyltin hydroxide (3). In the case of triphenyltin(IV) derivatives, 1 and 2, the values of the Mössbauer quadrupole splitting and the infrared data [Δν = (νas(OCO) −νs(OCO)) > 230 cm−1] are consistent with the presence of monomeric species in the solid state. X‐ray crystallographic analysis confirms their structures as consisting of monomeric species, featuring distorted tetrahedral environments around the tin atoms. In both structures, one CSnC angle is relatively opened compared with the two others, which may be linked to the relatively close approach of the non‐bonding oxygen of the carboxylate ligand to the tin center (Sn(1)O(2) = 2.659(1) Å and 2.773(1) Å in 1 and 2 respectively). NMR data show the presence of monomeric species in solution, as found in the solid state. A significant intramolecular hydrogen bond is noticed between the hydrogen atom of the N‐methylanthranilate ion and the non‐coordinating oxygen atom in 2 (H(1A)O(2) = 2.06 Å, N(1)H(1A)O(2) = 132°). Infrared and Mössbauer spectroscopy and X‐ray diffraction have shown that 3 has an infinite chain structure in which the central tin atom adopts a distorted trigonal bipyramidal coordination with two oxygen atoms in axial positions, the three carbon atoms of the methyl group occupying equatorial sites. The 3,5‐dinitrobenzoate anions act as bidentate bridging ligands and the SnC3 moieties are asymmetrically trans‐coordinated (SnO(1) and SnO(2): 2.181(1) and 2.501(2)). 13C and 119Sn NMR data reveal a cleavage of the infinite chain structure of 3 in solution; the 119Sn chemical shift value (124.0 ppm), in conjunction with the magnitude of the coupling constant [2J(119SnCH) = 58.8 Hz; 1J(119SnC) = 393.6Hz], is consistent with a tetrahedral environment around the tin center. Copyright © 2004 John Wiley & Sons, Ltd.