Some novel triorganotin(IV) derivatives of β, δ-triketones

Thirty triorganotin(IV) derivatives of the type R₃Sn(R′COCHCOCH₂COR″) and [R₃Sn]₂ (R′COCHCOCHCOR″) (where R = CH₃, C₂H₅, nC₃H₇, nC₄H₉ and C₆H₅ and R′ = R″ = CH₃, C₆H₅ or R′ = C₆H₅, R″ = CH₃) have been synthesised by the interaction of R₃SnCl with mono- or disodium salt of 2, 4, 6-heptanetrione, 1-phenyl-1, 3, 5-hexanetrione and 1, 5-diphenyl-1, 3, 5-pentanetrione in 1:1 and 2:1 molar ratios, respectively. The complexes have been examined by their molecular weight, IR, PMR and elemental analyses and their tentative structures assigned. Both “Z” and “E” forms have been identified in the 1:1 complexes in equilibrium with the enol form containing five coordinate tin. The 2:1 derivatives contain one five- and other four coordinated tin(IV) except the phenyl analogue where both the tins are five coordinated.     

Organotin(IV) complexes of dibasic tridentate Schiff bases containing ONO donor atoms

Organotin(IV) Schiff base complexes of the type (L)SnR₂ [where R?CH₃, C₆H₅ or CH₂CH₂CO₂ CH₃], (LH)Sn(C₆H₅)₃ and (L)SnCl(CH₂CH₂CO₂ CH₃) [where LH₂?2-N-salicylideneimino-2-methyl-1-propanol, derived from the condensation of salicylaldehyde and 2-amino-2-methyl-1-propanol] have been prepared and characterized on the basis of their elemental analyses, IR, ¹H, ¹³C and ¹¹⁹Sn NMR studies. In these mononuclear complexes the Schiff base acts either as a dianionic tridentate or as a monobasic bidentate moiety by coordinating through an alkoxy group, an azomethine nitrogen and a phenoxide ion to tin. Sulphur dioxide inserts in the tin–methyl/–phenyl bond in the above Schiff base complexes to give tin–O–sulphinates of formulae (L)RSn(SO₂R) and (LH)(C₆H₅)₂Sn(SO₂C₆H₅).     

丙酮酸异烟酰腙四核有机锡配合物的合成、表征及{[nBu2Sn(C9H8N3O3)O]SnBu3n}2的晶体结构

The tetranuclear alkyltin(Ⅳ) compounds {[R2Sn(C9H8N3O3)O]SnR3}2 [R=n-Bu (1), 4-CNC6H4CH2 (2),C6H5CH2 (3), 4-ClC6H4CH2 (4)] were prepared by the reaction of Schiff base ligand pyruvic acid isonicotinyl hydrazone with (R3Sn)2O in the corresponding molar ratio of 1:1. All compounds have been characterized by elemental analysis, IR and ^1H NMR spectra. The crystal structure of compound 1 was determined by X-ray single crystal diffractional analysis. This compound exhibits a dimeric structure containing distannoxane units with two types of the tin atoms. For the first tin atom, it appears to be seven-coordinated with a distorted pentagonal bipyramid geometry, and the other is five-coordinated with a distorted trigonal bipyramidal geometry. The molecules are packed in the unit cell in two-dimensional network structure through an interaction between the N atoms of the pyridine and the tin atoms of an adjacent molecule.     

Self-assembly of triorganotin(IV) or diorganotin(IV) moieties and 2-methylpyrazine-5-acid: Syntheses, characterizations and crystal structures of monomeric, polymeric or tetranuclear macrocyclic compounds

A series of diorganotin(IV) and triorganotin(IV) compounds of the type [R₂Sn(pca)₂ClSnR₃]₂ (RPhCH₂1, 2-ClC₆H₄CH₂2, 2-FC₆H₄CH₂3, 4-FC₆H₄CH₂4, 4-CNC₆H₄CH₂5, 4-ClC₆H₄CH₂6, 2,4-Cl₂C₆H₃CH₂7; Hpca2-methylpyrazine-5-acid), [(ⁿBu)₃Sn(pca)]_∞8, [(CH₃)₂Cl₂Sn(pca)Sn(CH₃)₂(pca)]_∞9, {[(ⁿBu)₂Sn(pca)]₂O}₂10 and {[Ph₂Sn(pca)]₃O₂[Ph₂Sn(OCH₃)]} 11 have been obtained by reactions of 2-methylpyrazine-5-acid with triorganotin(IV) chloride, diorganotin(IV) dichloride, and diorganotin(IV) oxide. All compounds were characterized by elemental, IR, and NMR spectra analyses. The crystal structure of compounds 1, 8-11 were determined by X-ray single crystal diffraction, which revealed that compound 1 was tetranuclear macrocyclic structures with seven-coordinate and five-coordinate tin atoms, compounds 8 and 9 were polymeric chain structures with five-coordinate and seven-coordinate tin atoms, compounds 10 and 11 were monomeric structures with six-coordinate and five-coordinate tin atoms.     

The synthesis,NMR (1H, 13C, 119Sn) and IR spectral studies of some di‐ and tri‐organotin(IV) sulfonates: X‐ray crystal structure of [(n‐C4H9)2Sn(OSO2C6H4CH3‐4)2·2H2O]

A number of alkyltin(IV) paratoluenesulfonates, R_nSn(OSO₂C₆H₄CH₃‐4)_4?n (n = 2, 3; R = C₂H₅, n‐C₃H₇, n‐C₄H₉), have been prepared and IR spectra and solution NMR (¹H, ¹³C, ¹¹⁹Sn) are reported for these compounds, including (n‐C₄H₉)₂Sn(OSO₂X)₂ (X = CH₃ and CF₃), the NMR spectra of which have not been reported previously. From the chemical shift δ(¹¹⁹Sn) and the coupling constants ¹J(¹³C, ¹¹⁹Sn) and ²J(¹H, ¹¹⁹Sn), the coordination of the tin atom and the geometry of its coordination sphere in solutions of these compounds is suggested. IR spectra of the compounds are very similar to that observed for the paratoluenesulfonate anion in its sodium salt. The studies indicate that diorganotin(IV) paratoluenesulfonates, and the previously reported compounds (n‐C₄H₉)₂Sn(OSO₂X)₂ (X = CH₃ and CF₃), contain bridging SO₃X groups that yield polymeric structures with hexacoordination around tin and contain non‐linear C? Sn? C bonds. In triorganotin(IV) sulfonates, pentacoordination for tin with a planar SnC₃ skeleton and bidentate bridging paratoluenesulfonate anionic groups are suggested by IR and NMR spectral studies. The X‐ray structure shows [(n‐C₄H₉)₂Sn(OSO₂C₆H₄CH₃‐4)₂·2H₂O] to be monomeric containing six‐coordinate tin and crystallizes from methanol–chloroform in monoclinic space group C2/c. The Sn? O (paratoluenesulfonate) bond distance (2.26(2) Å) is indicative of a relatively high degree of ionic character in the metal–anion bonds. Copyright © 2003 John Wiley & Sons, Ltd.     

Synthesis,characterization and in vitro antitumour activity of di‐ and tri‐organotin derivatives of fenbufen

The di‐ and tri‐organotin derivatives of fenbufen (4‐(4‐biphenyl)‐4‐oxobutyric acid), [{(n‐C₄H₉)₂Sn(OCOCH₂CH₂COC₆H₄C₆H₅‐4)}₂O]₂ ( 1 ) and R₃SnOCOCH₂CH₂COC₆H₄C₆H₅‐4 (R?C₆H₅, 2 ; c‐C₆H₁₁, 3 ; C₆H₅C(CH₃)₂CH₂, 4 ), have been prepared and characterized by means of elemental analysis, IR and NMR (¹H, ¹³C and ¹¹⁹Sn) spectroscopies. The crystal structure of 1 , bis[4‐(4‐biphenyl)‐4‐oxobutyrato]tetra‐n‐butyldistannoxane, has been determined and it is a centrosymmetric dimer with two distinct types of carboxylate moieties and tin atoms with distorted trigonal bipyramidal geometries. The in vitro antitumour activity of 1 and 2 against two human tumour cell lines was found to be higher than that for cis‐platin used clinically. Copyright © 2005 John Wiley & Sons, Ltd.     

Syntheses,spectroscopic characterizations and crystal structures of diorganotin(IV)-oxo-carboxylates with 2-pyrazinecarboxylic acid or (2-pyrimidylthio)acetic acid

Eight diorganotin(IV)-oxo-carboxylates {[R₂Sn(O(O)CR′)]₂O}₂?·?Y (R′?=?C₄H₃N₂Y?= H₂OR?=?ⁿBu 1, Y?=?0 R?=?Me 2, Y?=?0 R?=?C₆H₅ 3, Y?=?0 R?=?C₆H₅CH₂ 4; R′?=?CH₂SC₄H₃N₂-2,6Y?=?0 R?=?ⁿBu 5, Y?=?CH₂Cl₂R?=?Me 6, Y?=?0 R?=?C₆H₅ 7, Y?=?0 R?= C₆H₅CH₂ 8) have been prepared in 1?:?1 molar ratios by reactions of diorganotin(IV) oxide with 2-pyrazinecarboxylic acid or (2-pyrimidylthio)acetic acid, respectively. All the complexes are characterized by elemental analysis, IR, ¹H NMR and ¹³C NMR spectra. Except for 2, 4 and 7, the complexes are also characterized by X-ray crystallography diffraction analyses, which reveal that the complexes adopt the familiar dicarboxylato tetraorganodistannoxane structural mode. Among them, the evident difference is that weak intramolecular interactions between Sn and N atoms are recognized in complexes 1 and 3. However, for complex 5 two different coordination modes are found in the same lattice.     

Synthesis,spectroscopic characterization and in vitro antitumour activity of di-n-butyltin and diethyltin trimethoxybenzoates: X-ray structure analysis of bis[di-n-butyl(3,4,5-trimethoxybenzoato)tin] oxide

Di-n-butyltin(IV) and diethyltin(IV) 2,3,4-, 2,4,5- and 3,4,5-trimethoxybenzoates [(CH₃O)₃C₆H₂COO]₂SnR [Type a] and {[(CH₃O)₃C₆H₂COO]R₂Sn}₂O [Type b] have been synthesized and characterized spectroscopically. The crystal structure of bis[di-n-butyl(3,4,5- trimethoxybenzoato)tin] oxide has been determined. The triclinic unit cell contains one centrosymmetric dimer; a = 15.919(2) Å, b = 11.711(3) Å, c = 13.475(1) Å, and α = 63.63(2)°, β = 67.49(1)°, γ = 76.61(2)°. The geometry of the dimer is very similar to that of bis[di-n-butyl(5-methoxysalicylatotin] oxide), with two different types of five-coordinate tin atoms and one central planar Sn₂O₂ ring.     

有机锡9-芴酮-4-甲酸酯的合成、结构及抗癌活性

合成了 3 个有机锡 9-芴酮-4-甲酸酯:三苯基锡 9-芴酮-4-甲酸酯[(C₆H₅)₃Sn(C₁₄H₇O₃)] (1)、三环己基锡 9-芴酮-4-甲酸酯[(C₆H₁₁)₃Sn(C₁₄H₇O₃)] (2)和三(2-甲基-2-苯基丙基)锡 9-芴酮-4-甲酸酯[(C₆H₅C(CH₃)₂CH₂)₃Sn(C₁₄H₇O₃)] (3)。通过元素分析、红外光谱、核磁共振谱(¹H、¹³C和 ¹¹⁹Sn)、热重分析进行了表征;用单晶X射线衍射方法测定了化合物的晶体结构,并对其进行了量子化学计算和体外抗癌活性研究。结果显示:化合物1为一维链状结构,中心锡原子为五配位的畸变三角双锥构型;化合物2和3均为单核分子,锡原子均为四配位的畸变四面体构型。化合物对人宫颈癌细(HeLa)、人肝癌细胞(HUH-7)、人非小细胞肺癌细胞(A549)、人肺腺癌细胞(H1975)和人乳腺癌细胞(MCF-7)都有较好的抑制活性。     

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.     

[5‐Bromo‐N‐(2‐carboxylatophenyl)salicylideniminato]dimethyltin(IV)

The structure of the title di­methyl­tin(IV) complex, [2‐(5‐bromo‐2‐oxido­benzyl­idene­amino)­benzoato‐κ³O,N,O′]di­methyl­tin(IV), [Sn(CH₃)₂(C₁₄H₈BrNO₃)], features centrosymmetric dimers disposed about a central Sn₂O₂ core. Each Sn centre has seven‐coordinate pentagonal–bipyramidal geometry, taking into account two moderately long Sn—O contacts about an inversion centre [2.679 (4) and 2.981 (4) Å]. The methyl groups are in an axial orientation.     

Synthesis and Characterization of Diorganotin Compounds {[R2Sn（ON =CHC6H5）]2O}2 and Crystal Structure of {[（C6H5CH2）2Sn（ON=CHC6H5）]2O}2

Introduction Dimeric tetraorganodistannoxanes are a kind of in-teresting organotin oxo clusters and have attracted con-siderable attention during the last several decades, in view of their unique structural features1-5 as well as their applications as biocides6,7 and in homogenous cataly-sis.8,9 In the solid state, they contain characteristic Sn4O2X2Y2 structural motifts with staircase or ladder arrangements, a planar four-membered Sn2O2 ring and, generally, penta-coordination around the tin…     

Organotin(IV) azepane dithiocarbamates: Synthesis and characterization of the first organotin(IV) complexes with seven-membered cyclic dithiocarbamates

Abstract

We report the synthesis and spectroscopic characterization of the first organotin(IV) complexes with cyclic seven-membered dithiocarbamate ligands: the azepane-1-carbodithioate and the homopiperazine-1,4-bis-carbodithioate with two different organotin entities, di-n-butyltin and tri-cyclohexyltin: [(C₄H₉)₂Sn{S₂CN(CH₂)₆}₂] (3), [(C₆H₁₁)₃Sn{S₂CN(CH₂)₆}] (4), and [(C₆H₁₁)₃Sn}₂ (μ-S₂CN(C₅H₁₀)NCS₂)] (5). Compounds (3–5) are air-stable both in solid-state and in solution, and were characterized by elemental analyses, IR, FAB⁺–MS, and multinuclear NMR (¹H, ¹³C, and ¹¹⁹Sn) spectroscopy. Their molecular structures were unambiguously established by single-crystal X-ray diffraction studies. The geometrical arrangement around the tin atom can be described as distorted octahedral for (3) and distorted trigonal bipyramid for (4) and (5). The coordination mode for both ligands is considered as asymmetric bidentate, as happens in other organotin(IV) dithiocarbamates. Furthermore, (4) and (5) do not exhibit intermolecular secondary interactions, while (3) presents intermolecular interactions between the tin and a sulfur atom with the reciprocally neighboring molecule, giving rise to a zig-zag polymeric structure.     

Synthesis and structural characterizations of diorganotin(IV) complexes with 2-pyrazinecarboxylic acid

Two types of diorganotin(IV) complexes {[R₂Sn(O₂CC₄H₃N₂)]₂O}₂ (R = n-octyl 1, 2-ClC₆H₄CH₂3, 2-FC₆H₄CH₂5, 4-FC₆H₄CH₂7) and R₂Sn(O₂CC₄H₃N₂)₂ (R = n-octyl 2, 2-ClC₆H₄CH₂4, 2-FC₆H₄CH₂6, 4-FC₆H₄CH₂8) were prepared by reactions of diorganotin oxide with 2-pyrazinecarboxylic acid. The complexes 1-8 are characterized by elemental analysis, IR and NMR (¹H, ¹³C, ¹¹⁹Sn) spectroscopies. The complexes {[(n-C₈H₁₇)₂Sn(O₂CC₄H₃N₂)]₂O}₂ (1) and (n-C₈H₁₇)₂Sn(O₂CC₄H₃N₂)₂ (2) are also determined by X-ray single crystal diffraction, which reveal that the endo-cyclic tin atom of complex 1, is seven-coordinate, and the exo-cyclic tin atom is hexa-coordinated geometry, while the complex 2 is seven-coordinated geometry. The nitrogen atom of the aromatic ring participates in the interactions with the Sn atom.     

Coordination behaviour of the 2‐(N,N‐dimethylaminomethyl)phenyl ligand towards the di‐t‐butylchlorotin(IV) moiety

{2‐(N,N‐Dimethylaminomethyl)phenyl}(di‐t‐butyl)tin(IV)chloride, {2‐[(CH₃)₂NCH₂]C₆H₄}Sn(t‐Bu)₂ Cl, has been prepared and characterized using NMR and crystallography. This is the first example of a triorganotin(IV) halide containing the 2‐[(CH₃)₂NCH₂]C₆H₄—group as a C,N‐chelating ligand with a weak intramolecular Sn—N interaction because of the steric hindrance of t‐butyl groups. The interatomic Sn—N distance is elongated to 2.904(14) Å and the central tin atom is distorted trigonal bipyramidal. Copyright © 2004 John Wiley & Sons, Ltd.     

The preparation and 119Sn and 19F NMR spectra of some trifluoromethylphenyltin(IV) compounds

The preparation of a series of new trifluoromethylphenyltin(IV) compounds, Bu_nSn(C₆H₄CF₃-3)_4-n, (C₆H₄CF₃-3)SnCl₃, (C₆H₄CF₃-2)SnCl₃, and some related adducts with 2,2¹-bipyridyl and 1,10-phenanthroline, is described. ¹¹⁹Sn and ¹⁹F chemical shifts have been determined, together with values of J(¹¹⁹Sn=F) and ³J(¹¹⁹Sn=H_itortho), and the possibility of a “through space” tinfluorine coupling mechanism is also discussed.     

有机锡9-芴酮-4-甲酸酯的合成、结构及抗癌活性

合成了3个有机锡9-芴酮-4-甲酸酯:三苯基锡9-芴酮-4-甲酸酯[(C₆H₅)₃Sn(C₁₄H₇O₃)](1)、三环己基锡9-芴酮-4-甲酸酯[(C₆H₁₁)₃Sn(C₁₄H₇O₃)](2)和三(2-甲基-2-苯基丙基)锡9-芴酮-4-甲酸酯[(C₆H₅C(CH₃)₂CH₂)₃Sn(C₁₄H₇O₃)](3)。通过元素分析、红外光谱、核磁共振谱(¹H、¹³C和¹¹⁹Sn)、热重分析进行了表征;用单晶X射线衍射方法测定了化合物的晶体结构,并对其进行了量子化学计算和体外抗...     

Crystallographic report: Bis[3‐(tri‐p‐tolyl)germyl‐3‐(o‐tolyl)‐propionato]dibutyltin(IV)

The crystal structure of [(p‐CH₃C₆H₄)₃GeCH(o‐CH₃C₆H₄)CH₂CO₂]₂Sn(C₄H₉)₂ consists of a monomer with the atoms of tin and germanium both occupying tetrahedral geometries. However, the tin atom is distorted towards a skew trapezoidal bipyramid geometry as a result of weakly chelating carboxylate ligands. Copyright © 2003 John Wiley & Sons, Ltd.     

Investigation of pharmacophore and antipharmacophore features of certain dimethyltin(IV) complexes of flexible N‐protected amino acids and fluorinated β‐diketone/β‐diketones

A set of pentacoordinated dimethyltin(IV) complexes of flexible N‐protected amino acids and fluorinated β‐diketone/β‐diketones was screened for their antibacterial activity against Pseudomonas aeruginosa , Staphylococcus aureus and Streptomyces griseus . These pentacoordinated complexes of the type Me₂SnAB (where : R = CH(CH₃)C₂H₅, A₁H; CH₂CH(CH₃)₂, A₂H; CH(CH₃)₂, A₃H; CH₂C₆H₅, A₄H; and BH = R'C(O)CH₂C(O)R″: R′ = C₆H₅, R″ = CF₃, B₁H; R′ = R″ = CH₃, B₂H; R′ = C₆H₅, R″ = CH₃, B₃H; R′ = R″ = C₆H₅, B₄H) were generated by the reactions of dimethyltin(IV) dichloride with sodium salts of flexible N‐protected amino acids (ANa) and fluorinated β‐diketone/β‐diketones (BNa) in 1:1:1 molar ratio in refluxing dry benzene solution. Plausible structures of these complexes were elucidated on the basis of physicochemical and spectral studies. ¹¹⁹Sn NMR spectral data revealed the presence of pentacoordinated tin centres in these dimethyltin(IV) complexes.     

Investigations on organotin,organolead, lead(IV), and lead(II) dithiolates

Bis(triorganometal) 1,2-dithiolates (R₃M)₂S₂R′ [(HS)₂R′ = C₇H₈S₂ for toluene-dithiol-3,4 (H₂TDT); M = Sn, Pb; R = Ph; or (HS)₂R′ = C₁₀H₁₄S₂ for 1,2-dimethyl-4,5-bis(mercaptomethyl)benzene (H₂DBB); M = Sn, R = CH₃, C₆H₅; M = Pb, R = C₆H₅], diorganometal 1,2-dithiolates R₂MS₂R′ [(HS)₂R′ = C₆H₆S₂ for 1,2-dimercaptobenzene (H₂DMB); M = Pb, R = CH₃, C₂H₅, C₆H₅; or (HS)₂R′ = H₂TDT; M = Sn, R = CH₃, C₆H₅; M = Pb, R = C₆H₅; or (HS)₂R′ = H₂DBB; M = Sn, R = CH₃, C₆H₅; M = Pb, R = CH₃, C₂H₂, C₆H₅; or (HS)₂R′ = C₈H₆N₂S₂ for 2,3-dimercaptoquinoxaline (H₂QDT); M = Pb, R = C₆H₅] and some lead(IV) and lead(II) dithiolates Pb(S₂R′)_n [(HS)₂R′ = H₂DMB, n = 2; (HS)₂R′ = H₂TDT, n = 2; (HS)₂R′ = H₂DBB, n = 1 or 2] have been prepared. Vibrational, ¹H NMR, and Mössbauer spectroscopic data are consistent with pentacoordination of tin in R₂SnTDT and with tetracoordination of tin in R₂SnS₂R′ and (R₃Sn)₂S₂R′ in the solid state. The soluble compounds are monomeric in solution. Coupling constants for the methyltin compounds indicate tetracoordination in solution.