Synthesis, spectral characterization and biological activities of Organotin(IV) complexes with <i>ortho</i>-vanillin-2-hydrazinopyridine (VHP)

Five new organotin(IV) complexes of ortho-vanillin-2-hydrazinopyridine hydrazone with formula [RnSnCl4–n(VHP)] [R = Me2, n = 2 (2);R = Ph2, n = 2 (3);R= nBu2, n = 2 (4);R = nBu, n = 2 (5) and R = 1, n = 0 (6)] have been synthesized by direct reaction of ortho-vanillin-2-hydrazinopyridine hydrazone [(VHP), (1)], base and organotin(IV) chloride(s) in absolute methanol. The hydrazone ligand [(VHP), (1)] and its organotin(IV) complexes (2-6) have been characterized by UV-Visible, FT-IR and 1H NMR spectral studies. Spectroscopic data suggested that in the complexes (2-4), the ligand (1) acted as a neutral bidentate ligand and is coordinated to the tin(IV) atom via the azomethine nitrogen and pyridyl nitrogen atoms, whereas the ligand (1) acted as a uninegative tridentate ligand and coordinated to the tin(IV) atom through phenolic-O, azomethine-N and pyridyl-N atoms in complexes (5-6). The toxicity of the ligand (1) and its organotin (IV) complexes (2-6) were determined against Artemia salina. Organotin(IV) complexes showed moderate activity against Artemia salina. The ligand (1) and its organotin(IV) complexes (2-6) were also tested against four types of bacteria namely Bacillus cereus, Staphylococcus aureus, Escherichia coli and Enterobacter aerogenes. All organotin(IV) complexes and the free ligand (1) showed better antibacterial activities against bacteria. Among the organotin(IV) complexes (2-6), diphenyltin(IV) complex (3) showed higher activity against the four types of bacteria.

Syntheses, Crystal Structures and Biological Activities of the 2-Oxo-3-phenylpropionic Acid Arylformylhydrazone Dibenzyltin Complexes

Two 2-oxo-3-phenylpropionic acid arylformylhydrazone dibenzyltin(IV)complexes{[C4H3O(O)C=N-N=C(PhCH2)COO](C6H5CH2)2Sn(CH3OH)}2(Ⅰ)and{[t-Bu-C6H4(O)C=N-N=C(PhCH2)COO](C6H5CH2)2Sn(CH3OH)}2(Ⅱ)have been synthesized and characterized by IR,1H,13C and 119Sn NMR spectra,HRMS,and elemental,thermal stability and single-crystal X-ray diffraction analyses.Complex I crystallizes in the triclinic system,space group P1 with a=9.0392(9),b=10.249(1),c=15.5762(15)?,α=98.605(1)°,β=103.765(1)°,γ=104.056(1)°,Z=2,V=1326.3(2)?3,Dc=1.511 Mg·m^–3,m(MoKa)=1.005 mm–1,F(000)=612,R=0.0206 and wR=0.0524.Complex Ⅱ belongs to triclinic system,space group P1,a=11.4643(3),b=11.8885(3),c=13.0362(4)?,α=73.800(1)°,β=71.679(1)°,γ=79.006(1)°,Z=2,V=1609.34(8)?3,Dc=1.381 Mg·m^–3,m(MoKa)=0.833 mm–1,F(000)=688,R=0.0244 and wR=0.0244.In vitro antitumor activities of both complexes were evaluated by MTT against three human cancer cell lines(NCI-H460,HepG2 and MCF7)and human cell lines(HL7702).Both complexes exhibit better antitumor activity.Furthermore,the interaction between both complexes and calf thymus DNA was studied with EB fluorescent probe.

Synthesis,Structure and Biological Activities of a Novel Anionic Organotin(Ⅳ)Complex{[(pClC6H4CH2)Sn(H2O)(Cl)2OCOCH(O)CH(O)CO2Sn(H2O)(Cl)2(p-ClC6H4CH2)]·2(HNEt3)}

A novel anionic organotin(Ⅳ) complex {[(pClCHCH)Sn(HO)(Cl)OCOCH(O)CH(O)COSn(HO)(Cl)(p-ClCHCH)]·2(HNEt)}(1) was synthesized by the reaction of di(p-chlorobenzy)tin dichloride with the D-tartaric acid in 2:1 molar in the presence of an organic base triethylamine. The structure was characterized by elemental analysis, IR, TG, XRD and single-crystal X-ray diffraction. It crystallizes in triclinic, P1 space group, with a = 0.7067(1), b = 1.9762(3), c = 2.2383(3) nm, α = 91.544(2)°, β = 90.075(2)°, γ = 90.110(2)°, V = 3.1247(7) nm~3, Z = 3, Dc = 1.621 g/cm~3, m(Mo Kα) = 16.29 cm–1, F(000) = 1530, R = 0.0394, wR = 0.1092,(Δρ)max = 1224 and(Δρ)min = –840 e/nm~3. The stabilities, orbital energies and composition characteristics of some frontier molecular orbitals of 1 have been carefully investigated with quantum chemistry calculation. In addition, the in vitro antitumor activity suggested that 1 had stronger inhibitory activity on H460, MCF7 than on A549.

Synthesis, Characterization and Antibacterial Activity of Cyclohexyltin Complexes of N-(3,5-Dibromosalicylidene)valine

Three cyclohexyltin complexes of N-（3,5-dibromosalicylidene）valine（H_2L）, Cy_3Sn（HL）（1）, Cy_2SnL（2）, and Cy2 SnL ·Cy_3Sn Cl（3）（Cy = cyclohexyl）, have been synthesized and characterized by elemental analysis, IR, and ~1H and ^（13） C NMR spectra. The crystal structures of 2 and 3 have been determined. Complex 2 belongs to the monoclinic system, space group P21/n with a = 21.250（8）, b = 10.837（4）, c = 23.050（8） ？, b = 93.193（9）°, V = 5300（3） ？~3, Z = 8, D_c = 1.659 g/cm^3, m = 4.004 mm^（-1）, F（000） = 2624, R = 0.0471 and wR = 0.1015. Complex 3 belongs to the monoclinic system, space group P21 with a = 10.3452（10）, b = 18.7665（18）, c = 12.1483（12） ？, b = 103.374（2）°, V = 2294.5（4） ？3, Z = 2, D_c = 1.542 g/cm^3, m = 2.923 mm^（-1）, F（000） = 1072, R = 0.0428 and wR = 0.0936. Complex 2 has a distorted trigonal bipyramidal geometry with the axial locations occupied by one carboxylate oxygen and a phenolic oxygen of the ligand, and 3 reveals that the two tin atoms are joined via the carbonyl atom of the ligand to form a mixed organotin binuclear complex. Bioassay results show that 1 and 2 have good in vitro antibacterial activity against Escherichia coli.

Synthesis of Five-coordinated Anionic Tin(Ⅳ) Complexes and Crystal Structure of [(i-Pr)_2NH_2][PhSn( μ~2-SCH_2COO)_2]

Four new five-coordinated anionic tin(Ⅳ) complexes with a form of [R_ n NH_ 4- n ][PhSn( μ 2-SCH_2COO)_2] were synthesized via the reaction of mercaptoacetic acid with phenyltin trichloride in the presence of different organic bases and characterized by means of IR, 1H NMR and MS spectroscopies. The crystal structure of [( i -Pr)_2NH_2] [PhSn( μ 2-SCH_2COO)_2] was determined by X-ray diffraction. In the crystal structure,the tin atom is five-coordinated and exists in trigonal bipyramid geometry with cell parameters a =1.1766(11) nm, b =1.3144(14) nm, c =1.3336(15) nm,β =90° and Z =4.

Diorganotin Complexes of N-[4-(Diethylamino)salicylidene]-(L)-tryptophane: Syntheses, Structures and Properties

Four chiral diorganotin complexes of N-[4-(diethylamino)salicylidene]-(L)-tryptophane,R2Sn[4-(Et2N)-2-OC6H3CH=NCH(CH2Ind)COO](Ind=3-indolyl;R=Me(1);Et,(2);n-Bu(3);Cy(cyclohexyl)(4)),have been synthesized and characterized by elemental analysis,IR,and 1H and 13C NMR spectra.The crystal structures of 1-CH3OH-CHCl3,2,3-CH3OH and 4-CH3CH2OH have been determined by single-crystal X-ray diffraction.The complexes crystallize in orthorhombic system with P212121 space group,and the tin atoms are in distorted trigonal bipyramidal geometry and form five-and six-membered chelate rings with the chiral ONO tridentate ligand N-[4-(diethylamino)salicylidene]-(L)-tryptophane.In the complexes,the molecules are connected into one-dimensional supramolecular chain by intermolecular N–H…O–H…O=C or N–H…O–C hydrogen bonds.The fluorescence spectrum indicates that the complexes may be explored for potential blue luminescent materials.Bioassay results show that 3 and 4 belong to the efficient cytostatic agents against A549 human tumor cell.

Synthesis, Spectral and Antimicrobial Studies of Bis (Cyclopentadienyl) Titanium (IV) Bis (O,O’-Dialkyl and Alkylenedithiophosphate) Complexes

A new complexes of Cp2Ti[S2P(OR)2]2 (where R = Et, Pr-n, Pr-i, Bu-i and Ph) and Cp2Ti[S2POGO]2 (where G = -CH2CMe2CH2-, -CH2CEt2CH2- and -CMe2CMe2-) were prepared by the dropwise addition of the appropriate O,O’-dialkyl or -alkylenedithiophosphoric acid to biscyclopentadienyl titanium dichloride in 1:2 molar ratio and refluxed in benzene solution. These novel deep red colored complexes were characterized by elemental analyses, molecular weight measurements and spectroscopic techniques (IR., NMR 1H, 13C and 31P NMR). These titanium (IV) dithio complexes have also been screened for their antibacterial activities.

Formation,Structure and In Vitro Antitumour Activity of a Novel Binuclear Organotin Complex

A 1：1 reaction of triphenyltin chloride with potassium N-[（3,5-dibromo-2-hydroxylphenyl）methylene]valinate in benzene led to the formation of a novel mixed organotin dinuclear complex, （HL）SnPh3oPh2SnL [L=2-O-3,5-Br2C6H3CH=NCH（i-Pr）COO], by means of a facile phenyl-tin bond cleavage process. In the complex, there are two distinct types of carboxylate moieties and a trans-O2SnC2N and a trans-O2SnC3 in distorted trigonal bipyramidal geometries were bridged by a carboxylate group. In vitro antitumor activity of the complex against three human tumour cell lines （HeLa, CoLo205 and MCF-7） was found to be much higher than cis-platin used in clinic.

Synthesis, spectral, 3D molecular modeling and antibacterial studies of dibutyltin (IV) Schiff base complexes derived from substituted isatin and amino acids

New dibutyltin(IV) complexes of Schiff base derived from 5-chloroindoline-2,3-dione, indoline- 2,3-dione with amino acids (tryptophan, alanine and valine) were synthesized and characterized by elemental analysis, IR, electronic spectra, conductance measurements, and biological activity. The analytical data showed that the Schiff base ligand acts as bidentate towards metal ions via the azomethine nitrogen and carboxylate oxygen by a stoichiometric reaction of M:L (1:2) to form metal complexes. NMR (1H, 13C and 119Sn) spectral data of the ligands and metal complex agree with proposed structures. The conductivity values between 14 - 27 ohm-1cm2mol-1 in DMF imply the presence of non-electrolyte species. 3D molecular modeling and analysis of bond lengths and bond angles have also been conducted for a representative compound, [Bu2Sn(L2)2], to substantiate the proposed structures. Antibacterial results indicate that the metal complexes are more active than the free ligands.

New Square-Pyramidal Oxovanadium (IV) Complexes Derived from Polydentate Ligand (L1)

New series of oxovanadium (IV) complexes isolated from 2,4,6-tris-(2-pyridyl)-1,3,5-triazine (L1) are incorporated and portrayed using spectroscopic (IR, UV-Vis, ESR, mass spectrometric), magnetic moment, thermal and cyclic voltammetry measurements. The results demonstrate that L1 acts in various styles of chelation with [V3O3(L1)(SO4)3(EtOH)1/2(H2O)3/2] 1), [VO(L1)(2,4-pentadionate)]·Cl·4HCl 2), [V2O2(L1)(SO4)2(EtOH)5/2] 3), [V2O2(L1)(SO4)2(EtOH)3/2(H2O)1/2] 4), [VO(L1)SO4 (H2O)3/2]·2.5H2O 5) and [V2O2(L1)(SO4)2(H2O)]·H2O 6). The values of magnetic moments and spectral studies suggest a square-pyramidal geometry around the V (IV) ion for all complexes. The molar conductance values suggest that the complexes are non-electrolyte, except the [VO(L1) (2,4-pentadionate)] Cl·4HCl. Molecular modeling calculates the bond length, bond angle, chemical reactivity, energy components (Kcal/mol) and binding energy (Kcal/mol) for the isolated complexes. The in vitro antibacterial studies of these complexes screened against pathogenic bacteria prove them as growth inhibiting agents. Antitumor activity is carried out in vitro on human mammary gland (breast) MCF-7 and cervical cancer cell-HeLa has shown that [VO(L1)SO4(H2O)3/2]·2.5 H2O and [VO(L1)(2,4-pentadionate)] Cl·4HCl complexes display the highest powerful activity between all of the investigated complexes.

Se(IV)在北山花岗岩上的吸附

采用批式法研究了粉碎的甘肃北山花岗岩样品(BS03, 600 m)对Se(IV)的吸附作用. 实验结果表明: 在pH 3-7范围内, Se(IV)的吸附分配比(Kd)基本不随pH变化; 当pH > 7时, Se(IV)在北山花岗岩上的Kd随pH的增大而减小. Se(IV)在北山花岗岩上的吸附不随离子强度变化. 北山地下水条件下的Ca2+(4.10×10-3 mo·lL-1)和SO42- (3.17×10-3 mo·lL-1)对Se(IV)的吸附没有影响. 此外, Se(IV)/Eu(III)/北山花岗岩三元吸附体系的实验结果表明, Se(IV) (1.46×10-5 mo·lL-1)和Eu(III) (3.33×10-6 mo·lL-1)在北山花岗岩上的吸附作用相互之间没有表观影响. 通过假定HSeO3-在广义的吸附位点≡SOH上发生了生成≡SHSeO3和≡SSeO3-的两个表面配位反应, 定量解释了Se(IV)的吸附实验结果.

单核四价锰配合物Mn^(IV)(salae)_2的合成和晶体结构

目的合成高价锰配合物并研究其晶体结构。方法席夫碱配体H2salae(水杨醛缩乙醇胺)与Mn(OAc)3.2H2O在甲醇-水混合溶剂中反应,溶液静置,溶剂挥发后得到单晶。结果配合物MnIV(salae)2的单晶属六方晶系,空间群R-3,晶胞参数:a=1.7907(1)nm,b=1.7907(1)nm,c=2.8162(3)nm,α=90°,β=90°,γ=120°,V=7.8201(1)nm3,Z=18,Mr=381.28,Dc=1.457 g/cm3。结论MnIV由两个席夫碱配体进行配位,每个配体提供两个氧原子和一个氮原子。中心锰IV处于八面体的配位环境中。不同单元的分子由分子间C—H…O氢键和C—H…π弱相互作用连接在一起,形成三维结构。

具有抗肿瘤免疫治疗作用的铂类药物研究进展

经典铂类药物是一类潜在的免疫调节剂,通过诱导免疫原性细胞死亡(ICD)来参与肿瘤免疫调节。因而可将铂类药物分子与免疫治疗药物分子或其药效团进行拼合或融合,提高协同抗肿瘤疗效。铂(Ⅱ)药物是临床化疗最常见药物,由于其副作用和耐药性等缺点,使其临床应用受限。铂(Ⅳ)配合物具有动力学惰性和优于铂(Ⅱ)配合物的药理作用机制受到广泛关注和研究。本文旨在总结近年来发表的具有免疫调节功能的抗肿瘤铂配合物,通过化疗协同免疫疗法提高抗肿瘤疗效,为具有免疫功能的铂类药物的进一步研发和未来临床应用提供依据。

四氯·两个二(2-乙基已基)硫醚合铂(IV)配合物的合成及其分子结构

用萃取法合成了[Pt(DEHS)_2Cl_4],对配合物进行了元素分析,摩尔电导,差热一热重和红外光谱等测试并经X射线单晶结构分析确定了配合物的结构。

Synthesis and Crystal Structure of a One-dimensional Infinite Chain Organotin Complex [(n-Bu)_3Sn(OCOC_5H_4NO)]_n

A novel organotin complex [（n-Bu）3Sn（OCOC5H4NO）]n has been synthesized and characterized by elemental analysis, IR and ^1H NMR. The crystal structure has been determined by X-ray single-crystal diffraction. The crystal belongs to monoclinic, space group P2 1/c with a = 8.982（2）, b = 17.908（4）, c = 13.219（3） A, β= 96.981（4）°, Z = 4, V= 2110.6（8） A^3, Dc = 1.347 g/cm^3, μ（MoKa） = 12.23 cm^-1, F（000） = 880, R = 0.0497 and wR = 0.1263. In the molecular structure of the title complex, the tin atoms are five-coordinated in a distorted trigonal bipyramidal geometry. A one-dimensional linear polymer is formed through an interaction between the O atoms of pyridine-3-carboxylic acid N-oxide and tin atoms of an adjacent molecule.

Syntheses and Crystal Structures of Two Diethyltin Complexes of N-Salicylidene-α-amino Acid

Two novel diethyltin（IV） complexes of N-salicylidenevaline （H2L1） and N-Sali- cylidenetryptophan （H2L^2）, Et2SrtL^1 1 and Et2SnL^2 2, were synthesized and characterized by elemental analysis, IR, ^1H NMR and X-ray single-crystal diffraction analysis. Complex 1 belongs to the trigonal system, space group R-3 with a = b = 19.2730（5）, c = 23.6890（13）A^°, V= 7620.4（5） A^°^3, Z = 6, Dc= 1.553 g/cm^3,μ= 1.518 mm^-1, F（000） = 3600, R = 0.0238 and wR = 0.0636. Complex 2 is of monoelinie system, space group P21/c with a = 13.7550（8）, b = 11.5425（7）, c = 12.7876（7）A^°, β= 93.585（1）°, V = 2026.3（2） A^°^3, Z = 4, Dc= 1.548 g/cm^3,μ = 1.286 mm^-1, F（000） = 976, R = 0.0298 and wR = 0.0722. Complex 1 is a cyclic trimer with a macrocyclic 12-membered ring structure formed by the bidentate bridging coordination of carboxylate group to tin atoms. The tin atom is six-coordinated in a distorted octahedral geometry. In complex 2, the distorted trigonal bipyramidal Et2SnL2 units are linked into polymeric chains by the weak Sn…O interaction involving Sn and the earbonyl O of an adjacent ligand, and the chains are further connected by intermolecular N-H…O hydrogen bonds to form a two-dimensional supramolecular structure.

Synthesis,Characterization and Crystal Structure of the Dimeric Organotin Compound:{[n-Bu_(2)Sn(O_(2)CCH_(2)CS_(2)NC_(4)H_(8))]_(2)O}_(2)

The title compound,{[n-Bu_(2)Sn(O_(2)CCH_(2)CS_(2)NC_(4)H_(8))]_(2)O}_(2),has been synthesized by the reaction of(tetrahydro-pyrrodithiolocarbamoylthio)acetic acid with the di-n-bubyltin oxide in1∶1molar ratio.The complex has been characterized by elemental analysis,IR and NMR.The crystal structure of it has been determined by X-ray single crystal diffraction.And the results showed that the crystal belongs to triclinic system with space group P1and some crystal parameters:a=1.2202(9)nm,b=1.3158(10)nm,c=1.3804(10)nm,α=111.215(9)°,β=99.357(9)°,γ=96.075(10)°,V=2.006(2)nm 3,Z=1,F(000)=908,μ=1.489mm^(-1),D c=1.474g·cm^(-3),R_(1)=0.0375,wR_(2)=0.0839.The complex has a centrosymmetric dimer structure mode with a four-membered central endo-cyclic Sn_(2)O_(2)unit in which two bridged oxygen atoms both connect with an exo-cyclic tin atom which has a distorted octahedron.Each of the endo-cyclic tin atoms exhibits a distorted trigonal bipyramid coordination geometry with an additional weak coordination carboxylate oxygen.Four carboxylate ligands are divided into two types.And two of them are bidentate and connecting to each of exo-cyclic tin atoms by using both oxygen atoms,whereas the others bridge to each pair of exo-and endo-cyclic tin atoms utilizing one oxygen atom only.CCDC:220513.

L-吡咯烷功能化Zr(IV)金属有机骨架配合物的合成和催化不对称Aldol反应研究

设计合成了L-脯氨甲胺三联苯-4,4’-二甲酸配体(H2L)及其Zr(IV)-金属有机骨架配合物Zr6O4(OH)4(L)6(I),并研究了配合物I催化对硝基苯甲醛和环己酮的不对称羟醛缩合反应,催化反应具有适中的产率(60%)和较低的对映选择性(1.5%),催化产物的dr值为26∶74(anti/syn),以顺式异构体为主.

Synthesis and Anion Recognition of a Novel Heterocyclic Organotin Complex

A novel heterocyclic hexacoordinate organotin(Ⅳ) complex, bis(O-vanillin)-semi ethylenediamino dibenzyltin (VEDBT) was synthesized by the reaction of dibenzyltin dichloride with bis(O-vanillin)-semiethyenediamine, its structure has been characterized by spectral methods. The electrodes using VEDBT as a neutral carrier show high selectivity for salicylate anions.

Synthesis,Crystal Structure and Biological Activities of Novel Di-n-butyl Tin Di-carboxylate

A novel macrocyclic complex 2{[（n-Bu2Sn）4O2-L2]2DMF} was synthesized by the reaction of 4-（1,2- dithioethylene）methylene-3,5-disoxo-1,6-heptadiene-1,7-dis-（o-formy~）-dis-p-phenoxyacetic acid（LH2, compound 1） with di-n-butyltin oxide. Compound 1 and complex 2 were characterized by elemental analysis, FTIR spectroscopy, and ~H NMR spectroscopy. The crystal structure of complex 2 was determined by single crystal X-ray diffraction analysis. There are two crystallographic independent molecules in complex 2, and each molecule structure is centro-symmetric and features a central rhombus cyclic Bu4Sn2O2 unit with two exocyclic Sn atoms linked at the O atoms of the four-membered ring. In molecule A, the four Sn atoms are five-coordinated. However, in molecule B, the four Sn atoms have two different coordination geometries, the endocyclic Sn atoms are five-coordinated and the exocyclic Sn atoms are four-coordinated. The dicarboxylate ligands in molecules A and B bridge exocylic or endocyclic tin atoms, forming two macroheterocycles with 26 atoms. Pilot studies have indicated that complex 2 has good anti- bacterial and antitumour activities.