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1.
New triorganotin(IV) derivatives of the general formula R3Sn(Umb) (where, R = Me, n-Bu and Ph; Umb = umbelliferone anion) have been synthesized using sodium salt method. Further, the adducts of the general formula R3Sn(Umb) · phen (where R = Me and Ph; phen = 1,10-phenanthroline) have also been synthesized by the interaction of the triorganotin(IV) derivatives of umbelliferone with 1,10-phenanthroline. The bonding and coordination behavior of these derivatives are discussed on the basis of IR, NMR (1H, 13C and 119Sn), and 119Sn Mössbauer spectroscopic studies. These investigations indicate that umbelliferone acts as a monoanionic bidentate ligand in R3Sn(Umb) coordinating through O(7) and O(1) in the solid-state. These polymeric R3Sn(Umb) derivatives (where R = Me and n-Bu) have been proposed to have a trans-trigonal bipyramidal geometry with the three R groups in equatorial positions, while the axial positions are occupied by a phenolic oxygen and the O(1) atom from the adjacent molecule. A pseudotetrahedral geometry has been suggested for Ph3Sn(Umb). A distorted octahedral geometry around tin has been proposed for R3Sn(Umb) · phen, in which umbelliferone anion acts as a monodentate ligand coordinating through phenolic oxygen O(7). The newly synthesized derivatives have been assayed for their anti-inflammatory, cardiovascular and anti-microbial activities. The average LD50 values >1000 mg kg−1 of these derivatives indicate their safety margin. Among all the compounds tested, Ph3Sn(Umb) · phen has been found to show potent anti-inflammatory activity with low mammalian toxicity and mild hypotensive activity.  相似文献   

2.
New organotin(IV) complexes of the general formula R3Sn(L) (where R=Me, n-Bu and HL=L-proline; R=Me, Ph and HL=trans-hydroxy-L-proline and L-glutamine) and R2Sn(L)2 (where R=n-Bu, Ph and HL=L-proline; R=Ph, HL=trans-hydroxy-L-proline) have been synthesized by the reaction of RnSnCl(4-n) (where n=2 or 3) with sodium salt of the amino acid (HL). n-Bu2Sn(Pro)2 was synthesized by the reaction of n-Bu2SnO with L-proline under azeotropic removal of water. The bonding and coordination behavior in these complexes have been discussed on the basis of IR and 119Sn M?ssbauer spectroscopic studies in the solid-state. Their coordination behavior in solution has been discussed with the help of multinuclear (1H, 13C and 119Sn) NMR spectral studies. The 119Sn M?ssbauer and IR studies indicate that L-proline and trans-hydroxy-L-proline show similar coordination behavior towards organotin(IV) compounds. Pentacoordinate trigonal-bipyramidal and hexacoordinate octahedral structures, respectively, have been proposed for the tri- and diorganotin(IV) complexes of L-proline and trans-hydroxy-L-proline, in which the carboxylate group acts as bidentate group. L-glutamine shows different coordination behavior towards organotin(IV) compounds, it acts as monoanionic bidentate ligand coordinating through carboxylate and amino group. The triorganotin(IV) complexes of L-glutamine have been proposed to have trigonal-bipyramidal environment around tin. The newly synthesized complexes have been tested for their antiinflammatory and cardiovascular activities. Their LD50 values are >1000 mg kg-1.  相似文献   

3.
Some new diorganotin(IV) derivatives of the formulae, R2SnL, where R=Me, n-Bu, Ph, and n-Oct, and L is the dianion of histidinylalanine (H2L-1) and histidinylleucine (H2L-2) have been synthesized by the reaction of R2SnCl2 and the preformed sodium salt of the respective dipeptides. The bonding and coordination behaviour in these derivatives are discussed on the basis of FT-IR, multinuclear 1H, 13C and 119Sn NMR and 119Sn M?ssbauer spectroscopic studies. These investigations suggest that dipeptides in R2SnL act as dianionic tridentate coordinating through the COO(-), NH2 and N(-)peptide groups. The 119Sn M?ssbauer studies, together with the NMR data, suggest a trigonal bipyramidal geometry around tin in R2SnL with the alkyl/aryl groups and Npeptide in the equatorial positions, while a carboxylic oxygen and the amino nitrogen atom occupy the axial positions.  相似文献   

4.
Some di- and triorganotin(IV) triazolates of general formula, R(4-n)SnLn (where n=2; R=Me, n-Bu and Ph; n=1; R=Me, n-Pr, n-Bu and Ph and HL=4-amino-3-methyl-1,2,4-triazole-5-thiol (HL-1); and 4-amino-3-ethyl-1,2,4-triazole-5-thiol (HL-2)) were synthesized by the reaction of R(4-n)SnCln with sodium salt of HL-1 and HL-2. The bonding and coordination behavior in these derivatives have been discussed on the basis of IR and 119Sn M?ssbauer spectroscopic studies in the solid state. Their coordination behavior in solution is discussed by multinuclear (1H, 13C and 119Sn) NMR spectral studies. The IR and 119Sn M?ssbauer spectroscopic studies indicate that the ligands, HL-1 and HL-2 act as a monoanionic bidentate ligand, coordinating through Sexo- and Nring. The distorted skew trapezoidal-bipyramidal and distorted trigonal bipyramidal geometries have been proposed for R2SnL2 and R3SnL, respectively, in the solid state. In vitro antimicrobial screening of some of the newly synthesized derivatives and of some di- and triorganotin(IV) derivatives of 3-amino-1,2,4-triazole-5-thiol (HL-3) and 5-amino-3H-1,3,4-thiadiazole-2-thiol (HL-4) along with two standard drugs such as fluconazole and ciprofloxacin have been carried out against the bacteria, viz. Staphylococcus aureus and Escherichia coli, and against some fungi, viz. Aspergillus fumigatus, Candida albicans, Candida albicans (ATCC 10231), Candida krusei (GO3) and Candida glabrata (HO5) by the filter paper disc method. The studied organotin(IV) compounds show mild antifungal activity as compared to that of fluconazole, however, they show almost insignificant activity against the studied Gram-positive (Staphylococcus aureas) and Gram-negative (Escherichia coli) bacteria as compared to that of standard drug, ciprofloxacin.  相似文献   

5.
Some tri- and diorganotin(IV) compounds of the general formula, RnSnL4-n (where n=2, R=Me, n-Bu and Ph; n=3, R=Me, n-Bu, n-Pr and Ph; HL=5-amino-3H-1,3,4-thiadiazole-2-thione) have been synthesized by the reaction of RnSnCl4-n (where n=2 or 3, R=Me, n-Bu, n-Pr and Ph) and the sodium salt of the ligand. Oct2SnL2 was obtained by the reaction of Oct2SnO with HL in a 1:2 molar ratio under azeotropic removal of water. The bonding and coordination behavior in these derivatives are discussed on the basis of IR, Far-IR, multinuclear (1H, 13C and 119Sn) NMR and 119Sn M?ssbauer spectroscopic studies. These investigations suggest that in all the compounds the ligand acts as monoanionic bidentate coordinating through ring N(3) and exocyclic S. Thermal studies of five compounds, viz., Ph3SnL, Me2SnL2, n-Bu2SnL2, Oct2SnL2 and Ph2SnL2 have been carried out in the temperature range 25-1000 degrees C using TG, DTG and DTA techniques under an atmosphere of dry nitrogen.  相似文献   

6.
New non-electrolytic triorganotin(IV) derivatives of dipeptides with general formulae R3Sn(HL), where R = Ph and HL = monoanion of glycylisoleucine (H2L-1), valylvaline (H2L-2), alanylvaline (H2L-3), leucylalanine (H2L-4), leucylleucine (H2L-5); R = n-Bu and HL = monoanion of glycylisoleucine (H2L-1) and leucylalanine (H2L-4); and R = Me and HL = monoanion of leucylalanine (H2L-4) have been synthesized and characterized on the basis of infrared, multinuclear 1H, 13C and 119Sn NMR and 119Sn M?ssbauer spectroscopic studies. These investigations suggest that all the ligands in R3Sn(HL) act as monoanionic bidentates coordinating through the COO- and NH2 groups. The 119Sn M?ssbauer studies, together with the NMR data, indicate that, for these polymeric derivatives, the polyhedron around tin in R3Sn(HL) is a trigonal-bipyramid with the three organic groups in the equatorial positions, while the axial positions are occupied by a carboxylic oxygen and the amino nitrogen atom from the adjacent molecule. The anti-inflammatory and cardiovascular activities and toxicity of all these compounds have been determined. Four of the complexes have also been screened against some of the chosen bacterial and fungal strains. The Ph3Sn(IV) compounds exhibit better anti-inflammatory and cardiovascular activities in comparison to the Me3Sn(IV) and n-Bu3Sn(IV) analogues. n-Bu3Sn(Gly-Ile) and Ph3Sn(Ala-Val) exhibit good antibacterial activity against all the chosen strains.  相似文献   

7.
Novel heteroscorpionate-containing tin and organotin(IV) complexes, [SnRnX3 − n(L)], R = Me, Bun, Ph, or cy; X = Cl, Br or I, n = 0, 1, 2 or 3; L = bis(pyrazol-1-yl)acetate (bpza) or bis(3,5-dimethylpyrazol-1-yl)acetate (bdmpza), have been synthesized and characterized by spectral (IR, 1H, 13C and 119Sn NMR, 119mSn Mössbauer) and analytical data. In [SnI3(bdmpza)], the ligand is fac-N,N′,O-tridentate, the three iodine atoms thus also fac about the six-coordinate tin(IV) atom. Neutral bpzaH reacts with BunSnCl3, PhSnCl3 and SnCl4 in Et2O in the absence of base, yielding 1:1 adducts [XSnCl3(bpzaH)] (X = R or Cl).  相似文献   

8.
Some organotin(IV) triazolates of general formula RnSn(L)4 − n (where R = Me, n-Bu and Ph for n = 2; R = Me, n-Pr and n-Bu for n = 3 and HL = 3-amino-5-mercapto-1,2,4-triazole) have been synthesized by the reaction of R2SnCl2/R3SnCl with NaL in 1:2/1:1 molar ratio. Whereas, Oct2SnL2 has been synthesized azeotropically by the reaction of Oct2SnO and HL in 1:2 molar ratio. As good single crystals were not obtained, a large number of experimental techniques, viz. UV/Vis, IR, far-IR, multinuclear (1H, 13C and 119Sn) NMR and 119Sn Mössbauer spectroscopic studies, were used to accomplish a definitive characterization and determination of their most probable structures. In these compounds triazole acts as a monoanionic bidentate ligand, coordinating through Sexo and N(4). The IR and 119Sn Mössbauer spectroscopic studies allow us to deduce a highly distorted cis-trigonal-bipyramidal structure for R3SnL and a distorted skew trapezoidal-bipyramidal structure for R2SnL2, in the solid state. However, 1H, 13C and 119Sn NMR spectral studies revealed that weak bonding between tin and N(4) is further weakened in the solution leading to pseudo-tetrahedral/tetrahedral structure.  相似文献   

9.
Abstract

New triorganotin(IV) derivatives of dipeptides with general formulae, R3Sn(HL), where R = Me and Ph, and HL is the monoanion of histidinylalanine and histidinylleucine, have been synthesized and characterized on the basis of infrared (IR), multinuclear NMR (1H, 13C, and 119Sn), and 119Sn Mössbauer spectroscopic studies. These derivatives exhibit distorted trigonal-bipyramidal geometry around tin in which dipeptide anion acts as bidentate ligand coordinating through carboxyl oxygen and amino nitrogen. Ph3Sn(HHis-Ala),

Ph3Sn(HHis-Leu), and previously reported Ph2Sn(His-Ala), Me2Sn(His-Ala), n-Oct2Sn(His-Ala), Me2Sn(His-Leu), n-Oct2Sn(His-Leu), Ph3Sn(HTyr-Phe), Ph2Sn(Tyr-Phe), Bu2Sn-(Tyr-Phe), and n-Oct2Sn(Tyr-Phe) along with standard drugs, viz. phenyl butazone and indomethacin were screened for in vivo anti-inflammatory activity and acute toxicity (LD50). Diorganotin(IV) derivatives are more active than triorganotin(IV) derivatives. Me2Sn(His-Leu) shows the highest activity.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.  相似文献   

10.
Five new monorganotin(IV) compounds with thiobenzoate ligand, [BuSn(SOCPh)2]2O (1), [BuSn(O)(SOCPh)]2 (2), BuSn(Cl)(SOCPh)2 (3), BuSn(Cl)2(SOCPh) (4) and [BuSn(OH)(Cl)(SOCPh)]2 (5) were synthesized and characterized by elemental analyses, IR, 1H and 13C NMR spectroscopy. 119Sn NMR spectroscopy was used to determine the coordination geometry around Sn(IV) in the cases of 2 and 4. 1, 2 and 5 are dimeric while 3 and 4 are monomeric. In all these molecules the thiobenzoate ion is coordinated only through its sulfur atom. Molecular structures of the compounds have been optimized by MM2 calculations. Semi-empirical quantum mechanical calculations (PM3 method) were performed to explain the monodentate-bonding pattern of thiobenzoate ligand.  相似文献   

11.
Two novel dinuclear organotin(IV) complexes [n-Bu2Sn(imda)(H2O)]2·Bipy (1) and [n-Bu2Sn(imda)(H2O)]2·Phen (2) [H2imda = iminodiacetic acid, Bipy = 2,2′-bipyridine and Phen = 1,10-phenanthroline] were synthesised and characterized employing IR, 1H, 13C, 119Sn NMR, and 119Sn Mössbauer spectroscopic and elemental analyses. Single crystal X-ray crystallography of 1 has confirmed that it is a binuclear Sn(IV) species formed via carboxylate bridges where each metal adopted a seven coordinate distorted pentagonal bipyramidal geometry. The iminodiacetate dianion (imda2−) acts as a potential tridentate [N,O,O] carboxylate bridging ligand. The packing revealed that the additional α-diimine (Bipy or Phen) does not coordinate to metal ion. However, its presence in the crystal lattice as spacer helps for the formation of a supramolecular framework by bringing the two binuclear species close enough through extensive H-bonding. The in vitro cytotoxicity of compounds 1 and 2 indicate better results than cisplatin against three tumor cell lines investigated.  相似文献   

12.
Two diorganotin(IV) complexes of the general formula R2Sn[Ph(O)CCH-C(Me)N-NC(O)Ph] (R=Ph, 1; R=Me, 2) have been synthesised from the corresponding diorganotin(IV) dichloride and the ligand 4-phenyl-2,4-butanedionebenzoylhydrazone(2−) (H2L), derived from benzoyl acetone and benzoyl hydrazide in methanol at room temperature in presence of triethylamine. The syntheses were performed under very mild conditions, at room temperature and without exclusion of air or moisture from the reaction vessel. Previously, rigorous conditions have been considered necessary for these species. The two compounds have been characterised by elemental analysis, IR and 1H, 13C, 15N, 119Sn NMR spectra, and their structures have been confirmed single crystal X-ray structure analysis. The central tin atom of both complexes adopts a distorted trigonal bipyramidal coordination with two ligand oxygen atoms in axial positions, the nitrogen atom of the ligand and two organic groups on tin occupying equatorial sites. 2 has crystallised with two crystallographically independent molecules in the asymmetric unit. The δ(119Sn) values for the complexes 1 and 2 are −151.5 and −146.8 ppm, respectively, thus indicating penta-coordinated tin centres.  相似文献   

13.

The two octahedral complexes SnCl4·2(O)PF(NR2)2 (R = Me or Et) were prepared from reaction of SnCl4 with the ligand (R2N)2P(O)F in anhydrous CHCl3. The new adducts have been characterized by elemental analysis, IR, and multinuclear (119Sn, 31P, 19F, and 1H) NMR spectroscopy. The NMR data show that the adducts exist in solution as a mixture of cis and trans isomers with markedly different proportions. When compared with previously described hexamethylphosphoramide (HMPA) and trimethylphosphate (TMPA) analogues, our results indicate that the cis isomer is the predominant species in solution. Low temperature 31P and 119Sn NMR spectra show that the compounds partially dissociate in dichloromethane.  相似文献   

14.
15.
New organotin(IV) ascorbates of the general formulae R(3)Sn(HAsc) (where R = Me , n-Pr, n-Bu and Ph) and R(2)Sn(Asc) (where R = n-Bu and Ph) have been synthesized by the reaction of R(n)SnCl(4-n) (where n = 2 or 3) with monosodium-l-ascorbate. The bonding and coordination behaviour in these complexes are discussed on the basis of UV-Vis, IR, Far-IR, (1)H and (13)C NMR, and (119)Sn Mossbauer spectroscopic studies. L-Ascorbic acid acts as a monoanionic bidentate ligand in R(3)Sn(HAsc) coordinating through O(1) and O(3). The Mossbauer studies together with IR and NMR studies suggest that for these polymeric derivatives, the polyhedron is trigonal bipyramidal around tin with three organic groups in the equatorial positions. In R(2)Sn(Asc), L-ascorbic acid acts as dianionic tetradentate ligand and a polymeric structure with octahedral geometry around tin with trans organic groups has been tentatively proposed. The complexes have been assayed for their anti-inflammatory and cardiovascular activity. Ph(2)Sn(Asc) has been found to show the highest activity among the studied complexes. It is suggested on the basis of potentiometric studies of Me(2)Sn(IV) and Me(3)Sn(IV) systems with L-ascorbic acid that under physiological conditions (pH = 7.0) Me(2)Sn(HAsc)(OH) (approximately 60%), Me(2)Sn(OH)(2) (approximately 40%) and Me(3)Sn(HAsc) (approximately 60%), Me(3)Sn(OH) (approximately 40%), respectively, are existing, which may be responsible for their biological activities.  相似文献   

16.
Abstract

Reaction of tri-n-butyl tin(IV) chloride with the sodium salt of Schiff bases [salicylidene-2-aminopyridine (sapH), salicylidene-2-amino-4-picoline (sapicH), salicylidene-2-methyl-1-aminobenzene (o-smabH), salicylidene-4-methyl-1-aminobenzene (p-smabH), salicylidene-1- aminobenzene (sabH), salicylidene-3-nitro-1-aminobenzene (snabH)] in MeOH-C6H6 mixture in 1:1 molar ratio produced complexes of the type [Bun 3Sn(sb)] (where sb = Schiff bases). All complexes obtained were characterized by elemental analysis (C, H, N, and Sn), infrared (IR), nuclear magnetic resonance (NMR; 1H, 13C, and 119Sn), and TOF-MS spectroscopic studies. These complexes were found to be monomeric, colored viscous liquids and are soluble in polar solvents (methanol, ethanol, DMSO, and DMF). On the basis of 119Sn NMR observations, a five coordination geometry around tin(IV) atom in these complexes is proposed tentatively.  相似文献   

17.
The diorganotin(IV) and triorganotin(IV) derivatives R2SnA (R = Me, n-Pr, n-Bu, n-Oct) and (R3Sn)2A [R = Me, Ph, cyclohexyl (Cyh); A = an anion of diphenic acid] have been prepared and characterized by elemental analysis, IR, 1H and 13C NMR spectroscopies. Tetrahedral tin forms a part of a diphenate cyclic ring in the diorganotin complexes with unidentate carboxylates, which have further been used for the synthesis of cyclic acid anhydrides. The soluble dinuclear triorganotin complexes (Me, Ph) possess symmetrically bonded carboxylates while the less soluble compound (Cyh3Sn)2A has two asymmetrically bonded carboxylates. All have a trigonal bipyramidal structure with R3Sn units remote from each other.  相似文献   

18.
Some novel lower homologues of diorganotin derivatives of germyl substituted propanoic acids with general formula [Ar(3)GeCH(R(1))CH(R(2))COO](2)SnR(2)(3), where Ar = p-CH(3)C(6)H(4), C(6)H(5), R(1) = p-CH(3)C(6)H(4), p-CH(3)OC(6)H(4), o-CH(3)OC(6)H(4), C(6)H(5), R(2) = H, CH(3), R(3) = CH(3), C(2)H(5) have been prepared by the condensation reaction of dialkyltin oxide and triarylgermyl(substituted) propanoic acid in 1 : 2 M ratio, respectively, and were characterized by IR, multinuclear ((1)H, (13)C, (119)Sn) NMR, (119 m)Sn M?ssbauer spectroscopy. The synthesized compounds were also screened for their toxicity and possible antibacterial, antifungal activities and found some encouraging results.  相似文献   

19.
A novel complex Zn(phen)(m-CBA)2(H2O) with m-chlorobenzoic acid (m-CBA), 1,10-phenanthroline (phen) and zinc chloride has been hydrothermally synthesized and characterized. Crystal data for this complex: triclinic, space group P1, a = 0.8361(5), b = 1.2455(7), c = 1.3107(7) nm, α = 115.637(8), β = 91.014(9), γ = 104.857(8)o, V = 1.1763(11) nm3, Dc = 1.623 g/cm3, Z = 2, F(000) = 584, GOOF = 1.078, the final R = 0.0453 and wR = 0.1192. Structure analysis shows that the zinc ion coordinates with two nitrogen atoms of one 1,10-phenanthroline molecule, three oxygen atoms from two m-chlorobenzoic acid molecules and one water molecule, giving a distorted square-pyramidal coordination geometry. The cyclic voltametric behavior of the complex was also investigated.  相似文献   

20.
The tetradendate macrocyclic ligands, [H2L-1 = 5,12-dioxa-7,14-dimethyl-1,4,8,11-tetraazacyclotetradeca-1,8-diene] and [H2L-2 = 6,14-dioxa-8,16-dimethyl-1,5,9,13-tetraazacyclohexadeca-1,9-diene] have been prepared by the condensation reaction of 1,2-diaminoethane and 1,3-diaminopropane, respectively, with ethyl acetoacetate in methanol at room temperature. The diorganotin(IV) complexes of general formula [R2Sn(L-1)/R2Sn(L-2)] (R = Me, n-Bu and Ph) have been synthesized by template condensation reaction of 1,2-diaminoethane or 1,3-diaminopropane and ethyl acetoacetate with R2SnCl2 (R = Me or Ph) or n-Bu2SnO in 2:2:1 molar ratio at ambient temperature (35 ± 2 °C) in methanol. The solid-state characterization of resulting complexes have been carried out by elemental analysis, IR, recently developed DART-mass, solid-state 13C NMR, 119mSn Mössbauer spectroscopic studies. These studies suggest that in all of the studied complexes, the macrocyclic ligands act as tetradentate coordinating through four nitrogen atoms giving a skew-trapezoidal bipyramidal environment around tin center. Since, the studied diorganotin(IV) macrocyclic complexes are insoluble in common organic solvents, hence good crystals could not be grown for single crystal X-ray crystallographic studies. Thermal studies of all of the studied complexes have also been carried out in the temperature range 0-1000 °C using TG, DTG and DTA techniques. The end product of pyrolysis is SnO2 confirmed by XRD analysis.  相似文献   

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