首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 31 毫秒
1.
The complexes of four oxime analogues of amino acids and peptides (containing {O,N} donor atoms) with Bu2SnO were prepared, with ligand to metal ratios of 1 : 1 or 1 : 2, by two different methods. The FT-IR and Raman spectra clearly demonstrated that the organotin(IV) moieties react with the {O,N} atoms of the ligands. It was found that in most cases the -COO- group is coordinated to the central metal ion in a monodentate mode. Complex formation was accompanied by a rearrangement of the hydrogen-bonding network existing in the ligands. The complexes probably have monomeric structures. Comparison of the experimental Mössbauer values with those calculated on the basis of the point charge model (pqs) formalism revealed that the organotin(IV) moiety has octahedral (oct) geometry, and in certain cases trigonal-bipyramidal (tbp) geometry too.  相似文献   

2.
A number of organotin(IV) complexes with pyridine mono- and dicarboxylic acids (containing ligating -COOH group(s) and aromatic {N} atoms) were prepared in the solid state. The bonding sites of the ligands were determined by means of FT-IR spectroscopic measurements. It was found that in most cases the -COO groups form bridges between two central {Sn} atoms, thereby leading to polymeric (oligomeric) complexes. On this basis, the experimental 119Sn Mössbauer spectroscopic data were treated with partial quadrupole splitting approximations. The calculations predicted the existence of complexes with octahedral (oh) and trigonal-bipyramidal (tbp) structures, but the formation of complexes with pentagonal-bipyramidal (pbp) structures could not be ruled out. Single-crystals of 2-picolinic and pyridine-2,6-dicarboxylic acid Bu2Sn(IV)2+ complexes were obtained. The X-ray diffraction studies revealed that the central {Sn} atoms are in a pbp environment with bond distances characteristic of organotin(IV) compounds. The two butyl groups are located in axial positions. 119Sn NMR measurements in dmso solution and in the solid state indicated that the polymeric structures of the complexes are not retained in solution. The results of the solid-state 119Sn NMR measurements for compounds 1a, 2a and 6a are in agreement with the structures predicted by Mössbauer spectroscopy and revealed by X-ray diffraction.  相似文献   

3.
A number of dibutyltin(IV) complexes of polyhydroxyalkyl carboxylic acids (O donor atoms) and amino acids (O,N donor atoms) were prepared in the solid state. The binding sites of the ligands were determined by means of FT-IR, Raman and 13C NMR spectroscopy. Partial quadrupole splitting calculations were utilized to determine the coordination geometry around the Sn(IV) centre by means of Mössbauer measurements. The results showed that in the solid state oligomeric complexes are formed, with the -COO- groups as bridges between the organometallic cations. The {Sn} atoms are mostly in trigonal bipyramidal surroundings. The Sn-O and Sn-C bond distances were determined by EXAFS measurements to be 207-234 and 295 pm, respectively. Evaluation of the pH-metric and NMR titration curves in Me2Sn(IV)-D-gluconic acid system revealed that the equilibria in aqueous solution are fairly complicated. In acidic solution, the formation of 1 : 1 and 1 : 2 -COO- coordinated species predominate, but deprotonation of the alcoholic -OH groups also starts at very low pH. In the pH range 5-9, NMR provides experimental evidence of ligand-exchange reactions without pH-metrically detectable proton release. In alkaline solution, further deprotonation processes occur, resulting in either alkoxo or mixed hydroxo complexes. The carboxylate coordination is expected for the amino acid ligands but the shift of the νN-H stretching vibrations in the FT-IR spectra demonstrated that the ammine group also binds to the metal ion in the solid Bu2Sn(IV)complexes.  相似文献   

4.
Nine complexes of tBu2Sn(IV)2+ were obtained in the solid state with ligands containing -COOH group(s) and aromatic {N} donor atom. The binding sites of the ligands were identified by FT-IR spectroscopic measurements. It was found that in most cases the -COO groups are co-ordinated in monodentate manner. Nevertheless, in some of our complexes, the -COO group forms bridges between two central {Sn} atoms resulting in the formation of an oligomeric structure, a motif that is characteristic only to the nicotinate compound. These pieces of information and the rationalisation of the experimental 119Sn Mössbauer nuclear quadrupole splittings, Δ, - according to the point charge model formalism - support the formation of octahedral (Oh) or trigonal bipyramidal (TBP) molecular structures. The X-ray diffraction analysis of one complex obtained as single crystal revealed the distortion of the TBP geometry towards square pyramidal (SP) one. This was rationalised by PM3 molecular modelling of the tBu2Sn(pdc) complex. In the asymmetric unit, the two chemically similar but symmetry independent molecules form pseudo-dimers, in which the Sn?Sn separation amounts to ca. 6.4 Å. The crystal lattice is stabilised by C-H?O hydrogen bonding between individual molecules.  相似文献   

5.
The complexes of two organic carboxylates (containing {O,O}-donor atoms) with Me2Sn(IV)Cl2, n-Bu2Sn(IV)Cl2, Bz2Sn(IV)Cl2, Oct2Sn(IV)O, Me3Sn(IV)Cl, n-Bu3Sn(IV)Cl, Ph3Sn(IV)Cl, Ph3Sn(IV)Cl, and Bz3Sn(IV)Cl having ligand-to-metal ratios of 1: 2 and 1: 1 were prepared by two different methods. The FT-IR spectra clearly demonstrated that organotin(IV) moieties react with {O,O}-atoms of the ligands. It was found that in all cases the COO group was acting as bidentate in the solid state. The 119Sn NMR data revealed that the organotin(IV) moiety has a tetrahedral geometry in non-coordinating solvents. The biological activity of these compounds was compared with that of their precursors, and all the synthesized compounds show significant antibacterial activity. The antifungal activity of the complexes against six plant pathogens has been estimated. The complexes display marked toxicity against these fungi and are more fungitoxic than free acids. The compounds have also shown significant cytotoxicity against Brine Shrimp (Artemia salina). The article was submitted by the authors in English.  相似文献   

6.
A summary is presented of the results obtained on metal complexes of carbohydrates (aldoses, ketoses and mono-, di- and polysaccharides) and their derivatives (aldonic and alduronic acids, polyalcohols, amino sugars, and amino acid sugar adducts). The structural parameters (coordination number, bond distance, and Debye–Waller factor) measured by extended X-ray absorption fine structure (EXAFS) spectroscopy obtained earlier on transition metals [Cu(II), Fe(III), Ni(II), Zn(II), Co(II), Ag(I), Mn in different oxidation states and organotin(IV)] complexes are discussed. In addition we report here the preparation of Bu2Sn(IV)2+ complexes of rutin {3-[6-O-(6-deoxy--L-mannopyranosyl)-(-D-glucopyranosyl)oxy]-2-(3,4-dihydroxyphenyl)-5,7-dihydroxy-4H-1-benzopyran-4-one} and quercetin (containing {O,O} donor atoms) in ligand to metal ratios of 1:1 and 1:2. The analytical data revealed the formation of well-defined complexes. The local structures of the complexes were determined by an EXAFS method. It was found that the Sn–O bond distances in the first coordination sphere are closed the values found in Et2Sn(IV) complexes with nonprotected carbohydrates.  相似文献   

7.
A number of complexes of ligands containing {O,N,S} donor atoms (2,3,4,6-tetra-O-acetyl-b-D-thioglucopyranoside, 1-thio-b-D-glucose, 2-aminomercaptopurine, 4-amino-2-mercaptopyrimidine and 2-amino-6-mercaptopurine-9-D-riboside) with di-n-butyltin(IV) oxide, diphenyltin(IV) oxide, tribenzyltin(IV) chloride, and trimethyltin(IV) chloride were prepared in the solid state. It was found that the complexes contain the organotin(IV) moiety and the ligand in a ratio of 1:1 or 2:1. The FTIR and Raman spectra clearly demonstrated that the organotin(IV) moieties react with the {S} atom of the ligands, while di-n-butyltin(IV) oxide is coordinated to the deprotonated hydroxy group. In several cases, the basic part of the ligands also participates in complex formation. Comparison of the experimental Mössbauer D values with those calculated on the basis of the pqs concept revealed that the organotin(IV) moiety has trigonal-bipyramidal geometry, and in certain cases tetrahedral geometry too. Some of the complexes contain the organotin(IV) cation in two different surroundings.  相似文献   

8.
Five novel organotin complexes with the anthraquinone dyes alizarin (1,2‐dihydroxyanthraquinone) and purpurin (1,2,4‐trihydroxyanthraquinone) were synthesized and characterized by elemental analyses, FTIR and NMR spectroscopy (1H, 13C and 119Sn). The crystal and molecular structures of four complexes were determined by X‐ray diffraction on single crystals: [Bu2Sn(aliz)(H2O)]·C2H5OH ( A1 ·EtOH), [Bu2Sn(aliz)(dmso)]2 ( A3 ), [(Bu2Sn)3O(Hpurp)2] ( P1 ) and [Bu2Sn(Hpurp)(dmso)]2 ( P2 ), where H2aliz = alizarin and H3purp = purpurin. The coordination mode of the ligands is identical to that found in their Al/Ca complexes, where they act as dianionic tridentate ligands forming five and six‐membered fused chelate rings. The coordination to the tin atoms occurs exclusively via the 1,2‐ phenolate oxygen and the adjacent quinoid oxygen atoms. The complexes A1 , A3 and P1 are dimers with hepta‐coordinated tin atoms in form of a slightly distorted pentagonal bipyramid. The trinuclear complex P2 contains two pentacoordinated and one heptacoordinated tin atoms.  相似文献   

9.
This study encompasses the synthesis and characterization of organotin(IV) derivatives of non-steroidal anti-inflammatory drug ibuprofen (IBF), viz. [(Me3Sn)(IBF)] ( 1 ), [(Bu3Sn)(IBF)] ( 2 ), [Ph3Sn(IBF)] ( 3 ), {[Me2Sn(IBF)]2O}2 ( 4 ) and [Bu2Sn(IBF)2] ( 5 ). The crystal structure of complex 3 , [Ph3Sn(IBF)], indicates a highly distorted tetrahedral (td) geometry with anisobidentate mode of coordination of the carboxylate group with tin atom, and a similar structure has been proposed for other two triorganotin(IV) derivatives. Moreover, the DFT (density functional theory) calculation and other studies have verified a dimer distannoxane type of structure for complex 4 , {[Me2Sn(IBF)]2O}2. Complex 5 has been found to exhibit a highly distorted octahedral geometry around the tin atom. To investigate the DNA binding profile of the synthesized complexes, viscosity measurement, UV–vis and fluorescence titrations were performed, which revealed an intercalative type of binding with DNA for IBF and complex 5 and external binding in case of the complexes 1 and 2 ; complexes 3 and 4 could not be studied owing to their insufficient solubility in tris buffer. Plasmid DNA fragmentation studies of IBF and complexes 1 , 2 and 5 indicate that they cleaved the pBR322 plasmid potentially. Further, the drugs IBF {2-[4-(2-methylpropyl)phenyl]propanoic acid}, MESNA (sodium 2-mercaptoethane-sulfonate), warfarin [2H-1-benzopyran-2-one,4-hydroxy-3-(3-oxo-1-phenylbutyl)], sulindac (2-{5-fluoro-1-[(4-methanesulfinylphenyl) methylidene]-2-methyl-1H-inden-3-yl}acetic acid) and their corresponding organotin(IV) complexes 1–19 (complexes 6–19 were synthesized/reported previously) were screened in vitro for cytotoxicity against human cancer cell lines viz. DU145 (prostate cancer), HCT-15 (colon adenocarcinoma), Caco-2 (colorectal adenocarcinoma), MCF-7 (mammary cancer), LNCaP (androgen-sensitive prostate adenocarcinoma) and HeLa (cervical cancer), through MTT reduction assay and the cause of cell death was investigated through acridine orange/ethidium bromide staining of cells and DNA fragmentation assay. The probable structure–cytotoxicity relationship is also discussed. The major role of apoptosis along with small necrosis was also validated by flow cytometry assay using annexin V–fluorescein isothiocyanate and propidium iodide analysis.  相似文献   

10.
A number of [Ph3Sn(IV)]+ complexes formed with ligands containing -OH (-CO), or -COOH group(s) and aromatic {N} donor atom have been prepared. The binding sites of the ligands were identified by FT-IR spectroscopic measurements. In the complexes containing hydroxy and carboxylate functions, the carboxylato group is coordinated to the organotin(IV) centres in monodentate or bridging bidentate manner. It was also found that in the hydroxypyridine and -pyrimidine complexes the [Ph3Sn(IV)]+ moiety in most cases reacts with the phenolic form of the ligands. The rationalisation of the experimental 119Sn Mössbauer nuclear quadrupole splittings, |Δexp| - according to the point charge model formalism - together with the FT-IR data support the formation of trigonal bipyramidal (Tbp) or octahedral (Oh) molecular structures. Furthermore, X-ray diffraction analysis has been performed on the triphenyltin(IV)-3-phenolato-2(1H)-pyridinone-O,O′ single crystals. The penta-coordinated tin center exhibits a Tbp geometry. In case of 2-picolinic acid, a trans-phenylation was observed during the complexation, resulting [Ph2Sn(IV)]2+ complex and Ph4Sn(IV).  相似文献   

11.
The organotin(IV) cations form complexes with ligands containing {O}, {N}, {S}, or {phosphorus(O)} donor atoms with various composition and stability. The emergence of new experimental techniques (EXAFS, multinuclear 1H-, 13C-, 119Sn-NMR, 119Sn Mössbauer, etc., spectroscopic techniques) provided useful information about the structure and stabilities of the complexes formed. We reviewed the literature on these type of complexes taking into account the biological aspects of the complexes discussed.  相似文献   

12.
Some five- and six-coordinated di and tri-n-butyl tin(IV) semi- and thio-semi carbazates have been synthesized. The characterization of these complexes, by IR, NMR (1H, 13C, 119Sn), 119Sn), 119Sn Mössbauer and Mass spectroscopies along with X-ray diffraction, reveals that complexes of biionic ligands of the type Bu2Sn L″ are five-coordinated having trigonal bipyramidal geometry. However, complexes of monoionic ligands of the type Bu2SnL′2 are six-coordinated in a distorted cis-octahedral geometry and Bu3SnL′ are five-coordinated with a trigonal bipyramidal structure. X-ray structural studies on the compound Bu2Sn(O.C6H4.CH:N.N.CS.NH2), show that it crystallizes in a monoclinic lattice with a = 16.90 Å, b = 9.71 Å, c = 8.60 Å, and β = 103°45′.  相似文献   

13.
Twenty-two n-butyltin(IV) and t-butyltin(IV) complexes of ligands containing an -OH (-CO) group or -OH and -COOH groups and an aromatic {N} donor atom were prepared by metathetical reactions. On the basis of the FT-IR and Mössbauer spectroscopic data, molecular structures were assigned to these compounds. The binding sites of the ligands were identified by means of FT-IR spectroscopic measurements, and it was found that in most cases the organotin(IV) moiety reacts with the phenolic form of these ligands. In the complexes with -OH and -COOH functions, the -COOH group is coordinated to the organotin(IV) centres in a monodentate manner. The 119Sn Mössbauer and the FT-IR studies support the formation of trigonal bipyramidal (TBP) and octahedral (Oh) molecular structures. Furthermore, X-ray diffraction analysis has been performed on the n-butyltin(IV)- and t-butyltin(IV)-8-quinol 8-olato-O,N single crystals. The hexacoordinated tin centres exhibit cis-octahedral geometry in both complexes.  相似文献   

14.
Complexes of adenosine and related compounds (adenosine-5’-monophosphate, adenosine-5’-triphosphate and pyridoxal-5-phosphate) with Bu2SnO and/or BuSnCl2 were prepared in the solid state. The compositions of the complexes were determined by standard analytical methods. It was found that the complexes contain the organotin(IV) moiety and the ligand in a ratio of 1:1. The FT-IR spectra demonstrated that Bu2SnO reacts with the D-ribose moiety of the ligands, while Bu2SnCl2 is coordinated to the deprotonated phosphate group. The basic part of the ligands does not participate directly in complex formation. Comparison of the experimental Mössbauer Δ (quadrupole splitting) values with those calculated on the basis of the pqs concept revealed that the organotin(IV) moiety has Tbp and in some cases also Th geometry. The adenosine complex contains the organotin(IV) cation in two different surroundings (Tbp and Th). The local structures of the complexes were determined by means of EXAFS measurements. At the same time a number of organotin(IV) complexes containing different organo moieties of calf thymus DNA were also prepared. Similarly as above, EXAFS data were obtained for these compounds and analyzed by using multishell models up to 300 pm. These results are the first structural data (bond lengths) on complexes formed with organotin(IV)-DNA and related compounds.  相似文献   

15.
Diorganotin(IV)-complexes of the N-nitroso-N-phenylhydroxylaminates (hereinafter cupf), Et2Sn(cupf)2 (1), Bu2Sn(cupf)2 (2), {[Bu2Sn(cupf)]2O}2 (3), t-Bu2Sn(cupf)2 (4) and Oc2Sn(cupf)2 (5, 6) were prepared and characterised by FT-IR and Mössbauer spectroscopic measurements. The binding modes of the ligand were identified by FT-IR spectroscopy, and it was found that the ligand is coordinated in chelating or bridging mode to the organotin(IV) center. The 119Sn Mössbauer and FT-IR studies support the formation of trans-Oh (1-6) structures. The X-ray diffraction analysis of 4 revealed that the tin centre is in a skew-trapezoidal geometry defined by four donors derived from the cupferronato ligands and two carbon atoms from the tin-bound tbutyl substituents. The 119Sn NMR investigations indicate that in solution 4 retains its hexacoordinated nature.  相似文献   

16.
Reaction of dibutyltin dichloride, dimethyltin dichloride, and tributyltin chloride with ligands derived from thiosemicarbazone and semicarbazone leads to the formation of a new series of organotin(IV) complexes of general formula R2SnCl2·L and R3SnCl·L (where L ligands derived from the condensation of thiosemicarbazide and semicarbazide with 4-hydroxy-3-methoxybenzaldehyde). The authenticity of these ligands and their metal complexes have been established on the basis of elemental analysis, conductance measurements, molecular weight determinations, infrared, 1H NMR, 13C NMR, 119Sn NMR, and UV spectral studies. These studies showed that the ligands coordinate to the metal atom in a bidentate. An octahedral structure is proposed for the organotin(IV) complexes. The ligands and its metal complexes are screened for their antimicrobial activities against some Gram-positive and Gram-negative bacteria, and fungus. The studies demonstrated that metalation can increase the antimicrobial activity rather than the free ligands.  相似文献   

17.
A series of dibutylbis{5-[(E)-2-(aryl)-1-diazenyl]-2-hydroxybenzoato}tin(IV) complexes, Bu2Sn(LH)2, have been prepared and characterized by 1H, 13C, 119Sn NMR and ESI mass spectrometry in solution. The structures of the complexes Bu2Sn(L1H)2 (1), Bu2Sn(L3H)2 (3), Bu2Sn(L4H)2 (4), and Bu2Sn(L6H)2 (6) (L = 5-[(E)-2-(aryl)-1-diazenyl]-2-hydroxybenzoate: aryl = phenyl (L1H), 3-methylphenyl (L3H), 4-methylphenyl (L4H) and 4-bromophenyl (L6H)) were determined by X-ray crystallography and 117Sn CP-MAS NMR spectroscopy in the solid state. In general, the complexes were found to adopt a skew-trapezoidal bipyramidal arrangement around the tin atom. In addition, there are weak bridging intermolecular Sn?O contacts in complexes 1 and 3, but not in 4 and 6, where one of the hydroxy oxygen atoms from a neighboring molecule coordinates weakly with the Sn atom, thereby completing a seventh coordination site in the extended Sn coordination sphere. The Sn?O distance is 3.080(2) and 3.439(2) Å in 1 and 3, respectively, which are significantly shorter than the sum of the van der Waals radii of the Sn and O atoms (∼3.8 Å). In 1, this Sn?O interaction links the molecules into polymeric chains. In 3, these interactions link pairs of molecules into head-to-head dimeric units. The in vitro cytotoxicity of compound 2 indicates better results than cisplatin and etoposide against seven well characterized human tumor cell lines.  相似文献   

18.
One dinuclear chlorodiphenyltin (IV) dithiocarbamate complex (1) and four mononuclear complexes of general formula Ph2Sn(S2CNR)Cl (2, 3, 5, and 6) have been synthesized and characterized both in solid-state and solution. X-ray structures for complexes 1, 3 and 6 demonstrated a five-coordination geometry around of tin atoms, in which dithiocarbamate ligand chelates asymmetrically the metal center. As shown by 119Sn NMR spectroscopy, five-coordination geometry observed in the solid-state remains in solution. The stability of these chlorodiphenyltin(IV) dithiocarbamate complexes in the presence of biologically relevant anions such as acetate, dicarboxylates of general formula ?OOC-(CH2)n-COO? (n = 2–8), dihydrogenphosphate, hydrogensulfate, and halides has been examined in acetonitrile solutions. For all of these organotin(IV) complexes the displacement of the coordinated ligands (i.e., chloride and dithiocarbamate) from the organotin(IV) moiety occurred in the presence of monoanions like acetate, dihydrogenphosphate, hydrogensulfate and fluoride. A stepwise mechanism for ligand exchange is proposed based on UV–Vis, 1H, 13C and 119Sn spectroscopic data, as well as mass spectrometry. From UV–Vis titration experiments it was found that dicarboxylates with small spacers like malonate and succinate, acted differently in the exchange of the dithiocarbamate group in comparison to other monoanionic O donor ligands or dicarboxylates with longer chains, perhaps by following an intramolecular displacement of the coordinated ligand.The lability of these organotin(IV) dithiocarbamate compounds in solution hampers their use as stably host for anions, however, by taking advantage of the intrinsic chromogenic properties of free dithiocarbamate anions, or by attaching dithiocarbamate groups to well-known fluorescent moieties such as antracene, these complexes can sense the presence of O-donor anions at very low concentrations by displacement of the metal-coordinated dithiocarbamate.  相似文献   

19.
Four new compounds of organic mono carboxylic acid, 3-maleimidopropionic acid; with Bu2Sn(IV)2+, Ph3Sn(IV)+ and Cychex3Sn(IV)+ having ligand to metal ratio 1:2 and 1:1 were prepared. The spectrophotometric techniques used for structure determination like 1H-, 13C- and 119Sn-NMR, FT IR and 119mSn Mössbauer have demonstrated that the organotin(IV) moieties establish chemical bonding with the ligand through carboxylic oxygen atom. The percent CHN analyses and MS data also corroborates the spectroscopic results. During in vitro LD50, anti-fungal, anti-bacterial and anti-yeast bioassays promising results were exhibited. In vitro anti-tumour activity assays against five human tumor cell lines, MCF-7 Breast cancer-EVSA-T Breast cancer-WiDr Colon cancer-IGROV Ovarian cancer-M226 Non small cell lung cancer and anti-inflammatory screenings furnished the significant toxicities of the title complexes. In addition the triorganotin(IV) complexes were comparatively less toxic than the diorganotin(IV) complexes.  相似文献   

20.
Two organotin (IV) derivatives, [Bu2‐ Sn(HO3PO‐i‐Pr)2]2 ( 1 ) and [Bu2Sn(HO3POPh)2]2 ( 2 ), have been prepared by reactions of di‐n‐butyltin oxide with the phenylphosphoric acid and isopropylphosphoric acid, respectively. Characterization of the complexes 1 and 2 was achieved using elemental analysis, IR, NMR (1H, 13C, 31P, and 119Sn) spectroscopy, and X‐ray crystallography diffraction analysis. The X‐ray data reveal that complexes 1 and 2 are dimers containing eight‐membered Sn2O4P2 inorganic ring. Interestingly, complexes 1 and 2 are further linked into 2D network through intermolecular O … Sn weak contacts and O H … O weak hydrogen‐bonding interactions. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 21:298–303, 2010; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20610  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号