Synthesis,Spectral, and 3D Molecular Modeling of Tin(II) and Organotin(IV) Complexes of Biologically Active Schiff Bases Having Nitrogen and Sulfur Donor Ligands

Reaction of tin(II) chloride and dimethyltin dichloride with Schiff bases derived from S-benzyldithiocarbazate leads to the formation of a new series of tin(II) and organotin(IV) complexes of general formula SnCl ₂ .L and Me ₂ SnCl ₂ .L (where L = Schiff bases are derived from the condensation of S-benzyldithiocarbazate with heterocyclic aldehydes). An attempt has been made to prove the structures of the resulting complexes on the basis of elemental analysis, conductance measurements, molecular weight determinations, infrared, and multinuclear magnetic resonance ( ¹ H, ¹³ C, and ¹¹⁹ Sn NMR) spectral studies. A few representative ligands and their tin complexes have also been screened for their antibacterial and antifungal activities and found to be quite active in this respect.     

Triorganotin(IV) Derivatives of Bidentate Schiff Bases: Synthesis and Spectral Studies

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.     

Synthesis and Characterization of Novel Trans-Mixed Diamine Platinum(II) and Platinum(IV) Complexes

A series of novel trans-mixed diamine platinum(II) and platinum(IV) complexes of type trans-[Pt^II(R-NH₂)(R'-NH₂)Cl₂] and trans -[Pt^IV(R-NH₂)(R'-NH₂)Cl₄] (where R-NH₂ = ethylamine or butylamine and R'-NH₂ = methylamine, propylamine, isopropylamine, pentylamine, or hexylamine) was synthesized and characterized using elemental analysis and infrared and ¹⁹⁵Pt nuclear magnetic resonance spectroscopic techniques.     

Studies on the reaction of organotin phenoxides with ethyl propiolate catalysed by triethylamine and tin(IV) chloride

Different tributyltin phenoxides react at room temperature with ethyl propiolate in benzene, in the presence of tin(IV) chloride, triethylamine and their mixture to give the derivatives of 3‐phenoxyacrylic acid ethyl ester. Exceptionally, 3‐(2‐hydroxyphenyl)acrylic acid ethyl ester and 3‐(2‐hydroxy‐5‐methylphenyl)acrylic acid ethyl ester have been obtained from the reaction of tributylphenoxytin and tributyl(p‐tolyloxy)tin, respectively catalysed by SnCl₄, and they have been easily hydrolysed to coumarin and 6‐methylcoumarin. Copyright © 2007 John Wiley & Sons, Ltd.     

Synthesis,Characterization, and Antibacterial Studies of Oxovanadium(IV) Complexes with Thiazole-Derived Schiff Bases

Oxovanadium(IV) complexes of Schiff bases, derived from 2-amino-4-phenyl thiazole/substituted 2-amino-4-phenyl thiazoles and thiophene-2-aldehyde have been synthesized and characterized on the basis of elemental analysis, molar conductance measurements, magnetic susceptibility data, and UV-visible, and IR spectral studies. All the complexes are monomeric possessing a 1:2 (metal:ligand) stoichiometry. On the basis of these data, a square pyramidal geometry has been assigned for the complexes. A few complexes have been subjected to thermal decomposition studies. The ligands and their metal complexes have been screened for their antibacterial activities.

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.     

Synthesis and Characterization of Diorganotin(IV) Complexes Bearing Binary Schiff‐Bases and Crystal Structure of nBu2SnL1

Four novel diorganotin(IV) complexes with general formula R₂SnL (R = nBu, PhCH₂) were synthesized from diorganotin dichlorides and binary Schiff‐bases (H₂L) containing N₂O₂ donor atoms in the presence of sodium ethoxide. The Schiff bases were prepared by reactions of o‐phenylenediamine with 3‐tert‐butyl‐2‐hydroxy‐5‐methylbenzaldehyde (H₂L¹) and salicylaldehyde (H₂L²) respectively. The compounds were characterized by elemental analyses, IR, and NMR spectroscopy. The solid‐state crystal structure of the compound nBu₂SnL¹ was determined by single‐crystal structural analysis.     

Untersuchungen über Zinn(IV)-alkoxide. II. Isolierung und Charakterisierung der Verbindung Sn3O(OiBu)10 · 2i-BuOH. Das erste Beispiel für ein partielles Hydrolyseprodukt eines Zinn(IV)-alkoxids

Investigations into Tin(IV) Alkoxides. II. Isolation and Characterization of the Compound Sn₃O(OⁱBu)₁₀₁₀ · 2i-BuOH. The First Example of a Partially Hydrolized Tin(IV) Alkoxide The partial hydrolysis product Sn₃O(OⁱBu)₁₀ · 2i-BuOH was obtained by slow hydrolysis of the reaction product of tin tetrachloride with sodium isobutoxide. The compound forms colourless, moisture sensitive crystals, which easily release the coordinated solvent molecules in dry air. Its crystal and molecular structure has been determinated by single crystal X-ray diffraction. The compound crystallizes in the triclinic space group P1 with a = 1363.5(7), b = 1462.7(10), c = 1637.7(7) pm, α = 95.40(5)°, β = 96.79(4)°, γ = 102.12(5)° and Z = 2. The crystal structure consists of discrete, trimeric molecules with octahedrally coordinated tin atoms which are connected to each other corresponding to the formulation Sn₃(μ₃-O)(μ₂-OⁱBu)₃(O¹Bu)₇ · (i-BuOH)₂ by three isobutoxide groups bridging two metal atoms and a single threefold bridging oxygen atom     

Synthesis and characterization of coordination compounds of organotin(IV) with nitrogen and sulfur donor ligands

The reactions of dimethyltin dichloride with nitrogen and sulfur donor ligands derived by condensation of S‐benzyldithiocarbazate with indol‐3‐carboxylaldehyde, thiophene‐2‐aldehyde and furfuraldehyde have been investigated in 1:1 and 1:2 molar ratios in anhydrous alcohol. These ligands act as mononegatively charged bidentate species and coordinate to the central tin(IV) atom through the thiosulfur by proton exchange with the azomethine nitrogen. The newly synthesized complexes have been characterized by elemental analysis, conductance measurements and molecular weight determinations. The mode of bonding and the geometry of the complexes have been suggested on the basis of infrared, electronic and ¹H, ¹³C and ¹¹⁹Sn NMR spectroscopy, and probable structures have been assigned to these complexes. A few representative ligands and their tin(IV) complexes have also been screened for their antifungal and antibacterial activities and found to be quite active in this respect. Copyright © 2001 John Wiley & Sons, Ltd.     

Some Tribenzyl Tin(IV) Complexes with Thiohydrazides and Thiodiamines. Synthesis,characterization and thermal studies

Tribenzyl tin(IV) chloride complexes of morpholine N-thiohydrazide (L¹), aniline-N-thiohydrazide (L²),N-(morpholine-N-thio)-1,3-propanediamine (L³) and (aniline-N-thio)-1,3-propanediamine (L⁴) of the type (C₆H₅CH₂)₃Sn(L)Cl (where L=L¹, L², L³ and L⁴) have been synthesised in dioxane and in H₂O and acetone mixture. These were characterized by C,H,N-analysis, UV, IR and ¹HNMR spectral studies. In both the complexes ligands act as bidentate, coordinating through sulphur and terminal nitrogen. The complexes are 1:1 metal ligand complexes. Various thermodynamic parameters have been calculated for the decomposition steps using TG/DTA curves in air as well as nitrogen atmosphere. This revised version was published online in July 2006 with corrections to the Cover Date.     

二[N,N-(1,5-亚戊基)氨荒酸]二氯化锡和二(对氟苄基)氯化锡N,N-(1,5-亚戊基)氨荒酸酯的合成、表征及晶体结构

合成了二[N,N-(1,5-亚戊基)氨荒酸]二氯化锡和二(对氟苄基)氯化锡N,N-(1,5-亚戊基)氨荒酸酯.用X射线单晶衍射测定了这两个化合物的晶体结构.化合物1为单斜晶系,空间群P21, a=0.8635(5) nm, b=0.8842(5) nm, c=1.2942(7) nm, β=102.177(9)°, Z=2, V=0.9659(9) nm3, Dc=1.719 g/cm3, μ=2.024 mm-1, R=0.0428, wR=0.0918.化合物2正交晶系,空间群Pbca, a=1.3616(13) nm, b=1.1679(11) nm, c=2.7603(3)nm, Z=8, V=4.389(7) nm3, Dc=1.612 g/cm3, μ=1.498 mm-1, R=0.0355, wR=0.0887.在化合物1中,锡原子呈六配位畸变八面体构型,化合物2的锡原子呈五配位畸变三角双锥构型.     

Synthesis and characterization of uranium (IV) phosphate-hydrogenphosphate hydrate and cerium (IV) phosphate-hydrogenphosphate hydrate

A new uranium (IV) phosphate of proposed formula U₂(PO₄)₂HPO₄·H₂O, i.e. uranium phosphate-hydrogenphosphate hydrate (UPHPH), was synthesized in autoclave and/or in polytetrafluoroethylene closed containers at 150 °C by three ways: from uranium (IV) hydrochloric solution and phosphoric acid, from uranium dioxide and phosphoric acid and by transformation of the uranium hydrogenphosphate hydrate U(HPO₄)₂·nH₂O. The new product appears similar to the previously published thorium phosphate-hydrogenphosphate hydrate Th₂(PO₄)₂HPO₄·H₂O (TPHPH). From preliminary studies, it was found that UPHPH crystallizes in monoclinic system (, , , β=91.67(3)° and ). Heated under inert atmosphere, this compound is decomposed above 400 °C into uranium phosphate-triphosphate U₂(PO₄)P₃O₁₀, uranium diphosphate α-UP₂O₇ and diuranium oxide phosphate U₂O(PO₄)₂.Crystallized cerium (IV) phosphate-hydrogenphosphate hydrate Ce₂(PO₄)₂HPO₄·H₂O (CePHPH) was also synthesized from (NH₄)₂Ce(NO₃)₆ and phosphoric acid solutions by the same method (monoclinic system: , , , β=91.98(1)° and ). When heating above 600 °C, cerium (IV) is reduced into Ce (III) and forms a mixture of CePO₄ (monazite structure) and CeP₃O₉.     

Tin(IV) Complexes of 1,5-Diphenylthiocarbazone and Thiosemicarbazide: Synthesis,X-Ray Characterization,and Biological Activity

Abstract

The reaction of Me₂SnCl₂ with dithizone or thiosemicarbazide produced two novel di-organotin derivatives in good yields, which were characterized by X-ray diffraction. The crystal structures show that the compounds present a distorted pentacoordinated tin(IV) metal center. The antimicrobial activity of the new compounds was studied against Gram-negative (Escherichia coli, Klebsiella pneumonia, Salmonella enteritidis) and Gram-positive (Staphylococcus aureus) bacteria, and the yeast Saccharomyces cerevisiae. It was observed that the coordination of tin metal has a pronounced effect on the microbial activities of the ligands. All the tin complexes have shown higher antimicrobial effect than the free ligands.

GRAPHICAL ABSTRACT     

Synthesis, Characterization and Crystal Structure of Chlorodibenzyltin(IV) Complex with Dithiomorpholinocarba-mate Ligand

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Bioactive versatile azomethine complexes of organotin(IV) and organosilicon(IV)

Diorganotin(IV) and diorganosilicon(IV) derivatives of the types R₂MCl(TSCZ) and R₂M(TSCZ)₂ (where TSCZ is the anion of a thiosemicarbazone ligand, R=Ph or Me and M=Sn or Si) have been synthesized and characterized by elemental analyses, molecular weight determinations and conductivity measurements. The mode of bonding has been established on the basis of IR and ¹H, ¹³C ²⁹Si and ¹¹⁹Sn NMR spectroscopic studies. Some of the representative complexes have also been evaluated for their antimicrobial effects on different species of pathogenic fungi and bacteria in vivoas well as in vitro.The results of these investigations are reported. © 1998 John Wiley & Sons, Ltd.     

二正丁基锡水杨醛缩对氨基苯甲酸酯配合物的合成、表征及结构研究

The title complex {[ⁿBu₂Sn(2-OHC₆H₄CH=NC₆H₄COO)]₂O}₂·2H₂O was synthesized by the reaction of N-(4-carboxyphenyl)-salicylideneimine with dibutyltin(IV) oxide in 1∶1 molar ratio. The compound has been characterized by elemental analysis, IR, ¹H NMR spectra and X-ray single crystal diffraction. It crystallizes in triclinic system with space group P1. The crystal data are: a=1.242 9(2) nm, b=1.261 3(2) nm, c=1.594 9(3) nm, α=102.06(2)°, β=92.884(3)°, γ=95.939(3)°, Z=2, D_c=1.342 g·cm^-3, F(000)=1 000, V=2.425 2(7) nm³, R₁=0.041 5, wR₂=0.104 4. The compound is in centro-symmetric dimer structure mode with a four-member central endo-cyclic Sn₂O₂ unit in which the bridging oxygen atoms are tri-coordinated. All the tin atoms are five-coordinated with geometry of distorted trigonal bipyramid. CCDC:286105.     

Synthesis and Characterization of Some New Organoantimony(III) Derivatives of N,S Donor Bifunctional Tetradentate Schiff Bases

Reactions of triphenylantimony(III) with the corresponding Schiff bases in equimolar ratios yield the phenylantimony(III) derivatives, PhSb[RC(NC 6 H 4 S)CH 2 (NC 6 H 4 S)CCOOCH 3 ] (R = C 6 H 5 , 4-ClC 6 H 4 , 4-BrC 6 H 4 , and 4-CH 3 C 6 H 4 ). These derivatives have been characterized by elemental analyses, molecular weight measurements, and IR as well as NMR ( 1 H and 13 C) spectral studies which reveal a five coordination around the central antimony atom.     

Antimicorbial effects of newly synthesized organotin(IV) and organolead(IV) derivatives

Triorganotin(IV) and triorganolead(IV) derivatives of the types Me₃Sn(SCZ) and Ph₃Pb(SCZ) (where SCZ^? is the anion of a semicarbanzone ligand) have been synthesized by substitution reactions of trimethyltin chloride and triphenyl-lead chloride with semicarbazones derived from heterocyclic ketones. The resulting complexes have been characterized by elemental analyses, molecualr weight determinations and conductivity measurements. The mode of bonding has been established on the basis of infrared and ¹H, ¹³C and ¹¹⁹Sn NMR spectroscopic studies. Some respresentative complexes have also been evaluated for their antimicrobial effects on different species of pathogenic fungi and bacteria; the results of these investigations have been reported in the present paper.     

Synthesis, Spectroscopic Properties and Crystal Structures of Dibenzyltin（IV） Dithiobenzoate and Chlorodibenzyltin（IV） Thiobenzoate

Two dibenzyltin(IV) complexes with thiobenzoate ligand, (PhCH2)2Sn(SOCPh)2 (1) and (PhCH2)2Sn(C1)SOCPh (2), have been synthesized by the reaction of dibenzyltin(IV) dichloride with thiobenzoic acid in the presence of organic base Et3N and characterized by IR, ^1H NMR spectroscopy and elemental analysis. Their crystal structures were determined by X-ray single crystal diffraction analysis. In the crystals of 1, the tin atom is six-coordinated in a distorted octahedron configuration. In the crystals of 2, the molecular packing in unit cell reveals that the two adjacent molecules are symmetrically linked to each other to form a dimer with intermolecular Sn…C1 distances of 0.3591 (2) nm and the tin atom is five-coordinated in a distorted trigonal bipyramid configuration.     

O-Alkyl Trithiophosphate Derivatives of Triorganotin(IV) and S-Alkyl Trithiophosphate Derivatives of Diorganotin(IV) Chloride

Reactions of triorganotin chlorides with potassium salt of O-alkyl trithiophosphate [ROP(S)(SK)₂; R = Me, Prⁱ, Ph] in 2:1 molar ratio in anhydrous benzene yield triorganotin O-alkyl trithiophosphate of the type ROP(S) [SSnR′₃]₂ R = Me, Prⁱ; Ph, R′ = Prⁿ, Buⁿ, Ph] which are found to be monomeric in nature. These complexes are soluble in common organic solvents. Similar reactions of diorganotin chloride with dipotassium salt of S-alkyl trithiophosphate yield diorganotin-S-alkyl trithiophosphate of the type [(RS)P(O)S₂]₂SnR′₂; R = Me, Prⁱ; R′ = Me, Et, Ph, which also are found to be monomeric in nature and are soluble in common organic solvents. The newly synthesized derivatives have been characterized by physicochemical and spectroscopic techniques, IR, NMR (¹H, ³¹P, and ¹¹⁹Sn).     

Simultaneous determination of Zr(IV) and Hf(IV) by CE using precolumn complexation with a [PW(11)O(39)](7-) ligand

A CE method was developed for the simultaneous determination of Zr(IV) and Hf(IV) at trace levels. A lacunary Keggin-type [PW(11)O(39)](7-) ligand reacted quantitatively with a mixture of trace amounts of Zr(IV) and Hf(IV) to form the so-called ternary Keggin-type anions [P(Zr(IV)W(11))O(40)](5-) and [P(Hf(IV)W(11))O(40)](5-) in 0.010 M monochloroacetate buffer (pH 2.2). Since both ternary anions possessed different electrophoretic mobilities and high molar absorptivities in the UV region, Zr(IV) and Hf(IV) were determined simultaneously with direct UV detection at 258 nm. Each peak height was linearly dependent on the concentration of Zr(IV) or Hf(IV) in the range of 5.0x10(-7)-1.0x10(-5) M; a detection limit of 2x10(-7) M was achieved. The utility of the proposed CE method was demonstrated for the simultaneous determination of Zr(IV) and Hf(IV) in natural water samples with satisfactory results.