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).     

Synthesis,characterization and biological studies of oxovanadium(IV) complexes with triazole‐derived Schiff bases

A series of triazole‐derived Schiff bases (L¹–L⁵) and their oxovanadium(IV) complexes have been synthesized. The chemical structures of Schiff bases were characterized by their analytical (CHN analysis) and spectral (IR, ¹H and ¹³C NMR and mass spectrometry) data, and oxovanadium(IV) complexes were elucidated by their physical (magnetic susceptibility and conductivity), analytical (CHN analysis), conductance measurements and electronic spectral data. The molar conductivity data indicate the oxovanadium(IV) complexes to be non‐electrolyte. The Schiff bases act as bidentate and coordinate with the oxovanadium(IV)‐forming stoichiometry of a complex as [M (L‐H)₂] where M = VO and L = L¹–L⁵ in a square‐pyramidal geometry. The agar well diffusion method was used for in vitro antibacterial screening against E. coli, S. flexenari, P. aeruginosa, S. typhi, S. aureus and B. subtilis and for antifungal activity against T. longifucus, C. albican, A. flavus, M. canis, F. solani and C. glaberata. The biological activity data show the oxovanadium(IV) complexes to be more antibacterial and antifungal than the parent Schiff bases against one or more bacterial and fungal strains. Copyright © 2009 John Wiley & Sons, Ltd.     

Chemistry and applications of organotin(IV) complexes of Schiff bases

Schiff bases are the most widely used versatile ligands, able to coordinate many elements and to stabilize them in various oxidation states. Recently, this class of compounds has been employed as models for biological systems, and in control of stereochemistry in six-coordinate transition metal complexes. Recently, the chemistry of organotin(IV) complexes of Schiff bases has also stemmed from their antitumour, antimicrobial, antinematicidal, anti-insecticidal and anti-inflammatory activities. Furthermore, organotin(IV) complexes of Schiff bases present a wide variety of interesting structural possibilities. Both aliphatic and aromatic Schiff bases in their neutral and deprotonated forms have been used to yield adducts and chelates with variable stoichiometry and different modes of coordination. This critical review (>155 references) focuses upon the chemistry and biological applications of organotin(IV) complexes of Schiff bases reported in the past 15 years. Thermal behavior of these complexes is also discussed.     

Synthesis,characterization and biological activities of organotin(IV) complexes with l-lysine monohydrate

Russian Journal of General Chemistry - The new organotin(IV) complexes have been synthesized by the reaction of l-lysine monohydrate with CS2 and R2SnCl2/R3SnCl. The organotin(IV) complexes and the...     

Synthesis,spectral, theoretical studies and in vitro antimicrobial activities of novel diphenyltin(IV) complexes of Schiff bases derived from phenacylamine

A series of new diphenyltin(IV) complexes of the type Ph₂SnL (L¹: N‐phenacyl‐5‐bromosalicylideneimine, Ph₂SnL¹; L²: N‐phenacyl‐3,5‐dichlorosalicylideneimine, Ph₂SnL²; L³: N–phenacyl‐4‐methoxysalicylideneimine, Ph₂SnL³) were synthesized and characterized by elemental analysis, IR, ¹H, ¹³C, ¹¹⁹Sn NMR spectroscopy and mass spectrometry techniques. The C―Sn―C angles in the complexes were calculated using equations with the ¹J(^117/119Sn―¹³C) values from ¹³C NMR spectra. The possible structures, NMR and electronic properties of the studied molecules were calculated through density functional theory and results compared with experimental data. All the complexes were found to be mildly active against several microorganisms and some fungi. Copyright © 2014 John Wiley & Sons, Ltd.     

Synthesis of coordination compounds of dibutyltin(IV) with Schiff bases having nitrogen donor atoms

The new dibutyltin(IV) complexes of Schiff bases is designed & synthesis from the interaction between various substituted amines and aromatic aldehyde with general formula Bu₂Sn(L^1-7)₂Cl₂. Where L¹: (E)-4-chloro-N-(thiophen-2-ylmethylene) aniline; L²: (E)-2-chloro-N-(3,4,5-trimethoxybenzylidene) aniline; L³: (E)-N-((1H-indol-3-yl) methylene)-4-chloro-2-nitroaniline; L⁴: (E)-4-nitro-N-(3,4,5-trimethoxybenzylidene) aniline; L⁵: (E)-N-(3,4,5-trimethoxybenzylidene) aniline; L⁶: (E)-4-nitro-N-(thiophen-3-ylmethylene) aniline; L⁷: (E)-4-chloro-2-nitro-N-(pyridin-3-ylmethylene) aniline. Analytical and spectroscopic methods, such as molar conductance measurement, UV–Vis, IR, NMR, and DFT studies, have been used to describe newly synthesised compounds. The DFT studies have also provided confirmation regarding the complexes' geometry. The results of the Tauc equation indicate that the fundamental band gap of the compound [Bu₂Sn(L⁵)₂Cl₂] is 2.670 eV, which is in agreement with the findings of DFT studies, which indicate that the band gap is 2.657 eV. The bactericidal effects of Schiff bases and their dibutyltin(IV) complexes were tested. The antibacterial activity of organotin(IV) complexes is enhanced in comparison to that of the free ligands.     

Synthesis and characterization of pentagonal bipyramidal organotin(IV) complexes of 2,6-diacetylpyridine Schiff bases of S-alkyl- and aryldithiocarbazates

New organotin(IV) complexes with empirical formula Sn(SNNNS)R₂, where SNNNS is the dianionic form of 2,6-diacetylpyridine Schiff bases of S-methyldithiocarbazate (H₂dapsme) or S-benzyldithiocarbazate (H₂dapsbz) and R = Ph or Me, have been prepared and characterized by IR, UV-Vis, NMR and Mössbauer spectroscopic techniques and conductance measurements. The molecular structures of the Sn(dapsme)R₂ (R = Ph and Me) have been determined by single crystal X-ray diffraction techniques. Both complexes have a distorted pentagonal-bipyramidal geometry in which the tin is coordinated by a dinegatively charged pentadentate chelating agent via pyridine nitrogen, two azomethine nitrogens, and two thiolate sulfurs. The five donors (N₃S₂) provided by the Schiff base occupy the equatorial plane close to a pentagonal planar array while the carbanion ligands occupy axial sites.     

Synthesis and spectroscopic studies of new organotin(IV) complexes with tridentate N- and O-donor Schiff bases

The Schiff bases H₂L¹ and H₂L² have been prepared by the reaction of 2-amino-4-chlorophenol with pyrrole-2-carbaldehyde and 2-hydroxy-1-naphtaldehyde, respectively, and HL³ from reaction of 2-(aminomethyl)pyridine with 2-hydroxy-1-naphtaldehyde. Organotin complexes [SnPh₂(L¹)] (1), [SnPh₂(L²)] (2), [SnMe₂(L²)] (3) and [SnPhCl₂(L³)] (4) were synthesized from reaction of SnPh₂Cl₂ and SnMe₂Cl₂ with these Schiff bases. The synthesized complexes have been investigated by elemental analysis and FT-IR, ¹H NMR and ¹¹⁹Sn NMR spectroscopy. In complexes the Schiff bases are completely deprotonated and coordinated to tin as tridentate ligands via phenolic oxygen, pyrrolic, and imine nitrogens in 1, two phenolic oxygens and imine nitrogen in 2 and 3, and phenolic oxygen, imine and pyridine nitrogens in 4. The coordination number of tin in 1, 2, and 3 is five and in 4 is six.     

Synthesis,characterization, DNA cleavage and in vitro antimicrobial activities of copper(II) complexes of Schiff bases containing a 2,4-disubstituted thiazole

Six Cu(II) complexes of Schiff base ligands of arylidene-2-(4-(4-bromo/methoxy-phenyl)thiazol-2-yl) hydrazines have been synthesized, characterized and screened for DNA cleavage and antimicrobial activities. The chemical structures of the complexes were deduced by physicochemical and spectroscopic methods. Elemental analyses indicated that the stoichiometry of the complexes is CuL₂ (L = Schiff base ligand). The DNA cleavage activities of the complexes were evaluated by agarose gel electrophoresis in the presence and absence of oxidant (H₂O₂) and free radical scavenger (DMSO). All the six complexes showed significant nuclease activity in the presence of H₂O₂, and two of the complexes showed moderate nuclease activity even in the absence of oxidant. The complexes did not show nuclease activity in the presence of free radical scavenger. The compounds were tested for activity against selected bacteria and fungi.     

Homobimetallic organotin(IV) complexes with succinohydrazide Schiff base: Synthesis,spectroscopic characterization,and biological screening

Russian Journal of General Chemistry - Six new bis-diorganotin(IV) complexes, [(Me2Sn)2L] (1), [(Et2Sn)2L] (2), [(n-Bu2Sn)2L] (3), [(Ph2Sn)2L] (4), [(n-Oct2Sn)2L] (5), and [(tert-C4H9)2Sn)2L] (6),...     

Kinetic studies of the interaction between organotin(IV)chlorides and tetraaza Schiff bases: Synthesis and characterization of some novel tin(IV) Schiff base complexes

In this article the kinetics of the interaction between the teteraaza Schiff bases as donor with organotin(IV)chlorides as acceptor was studied in acetonitrile. Teteraaza Schiff bases are (Me₄‐Bzo₂[14]tetraeneN₄) (tmtaa), (Me₄‐4‐CH₃Bzo₂[14]tetraeneN₄) (Metmtaa), (Me₄‐4‐ClBzo₂[14]tetraeneN₄) (Cltmtaa), i.e., [(Me₄‐Bzo₂[14]tetraeneN₄)] means that (5,7,12,14‐tetramethyldibenzo[b,i][1,4,8,11] tetraazacyclotetradecine) (tmtaa) and organotin(IV)chlorides are methyltin(IV) trichloride, phenyltin(IV)trichloride, dimethyltin (IV)dichloride, diphenyltin(IV) dichloride, and dibutyltin(IV)dichloride. The kinetic parameters and the second‐order k₂ rate constants show the donor properties of tetraaza Schiff bases as Me₄‐4‐CH₃Bzo₂[14]tetraeneN₄ > Me₄‐Bzo₂[14]tetraeneN₄ > Me₄‐4‐ClBzo₂[14]tetraeneN₄ and also the acceptor properties of organotin(IV)chlorides as PhSnCl₃ > MeSnCl₃ > Ph₂SnCl₂ > Me₂SnCl₂ > Bu₂SnCl₂. An excellent linearity of k_obs vs. the molar concentration of the acceptor, the high span of k₂ values, the large negative values of ΔS^≠, and the low ΔH^≠ values suggest an associative (A) mechanism for the acceptor–donor interaction. © 2011 Wiley Peiodicals, Inc. Int J Chem Kinet 43: 247–254, 2011     

Some divalent metal(II) complexes of salicylaldehyde‐derived Schiff bases: Synthesis,spectroscopic characterization,antimicrobial and in vitro anticancer studies

Mononuclear transition metal(II) complexes of the type M(L)₂?2H₂O (where M = Co, Ni, Cu, Zn) have been synthesized from uninegative Schiff base ligands (HL₁–HL₄) designed by condensation of 4‐fluorobenzylamine with 2‐hydroxy‐1‐naphthaldehyde/3,5‐dichlorosalicylaldehyde/3,5‐dibromosalicylaldehyde/3‐bromo‐5‐chlorosalicylaldehyde. The compounds were successfully characterized using spectroscopic and physiochemical methods together with elemental analysis. Spectroscopic elucidation indicates a monobasic bidentate nature of ligands coordinated via deprotonated phenolic oxygen and azomethine nitrogen atom which suggests an octahedral geometry around the central metal ions. The complexes and ligands were screened for their in vitro antimicrobial activity against bacterial and fungal strains, the zinc(II) complexes being more active against the tested microbial strains. Further, the metal complexes were found to be more active than the uncomplexed ligands due to chelation process and, moreover, the complexes were more active against fungal strains than bacterial strains. Cytotoxic activities of all compounds were evaluated towards human alveolar adenocarcinoma epithelial cell line (A549), human breast adenocarcinoma cell line (MCF7), human prostate cancer cell line (DU145) and one normal human lung cell line (MRC‐5) using MTT colorimetric assay with doxorubicin as a standard. The zinc complexes were most active against the cancer cell lines and also found to be less toxic against MRC‐5 normal cell line than standard doxorubicin.     

Synthesis,spectroscopic characterization,thermal behaviour,in vitro antimicrobial and anticancer activities of novel ruthenium tricarbonyl complexes containing monodentate V‐shaped Schiff bases

The interaction of Ru₃(CO)₁₂ with a novel family of monodentate V‐shaped Schiff base ligands (L^1–4; L¹: (E)‐1‐(4‐((4‐bromobenzylidene)amino)phenyl)ethanone, L²: (E)‐1‐(3‐(4‐(dimethylamino)benzylideneamino)phenyl)ethanone, L³: (E)‐1‐(4‐(4‐(dimethylamino)benzylideneamino)phenyl)ethanone, L⁴: (E)‐1‐(3‐(3,4‐dimethoxybenzylideneamino)phenyl)ethanone) in air under atmospheric pressure afforded the novel complexes [Ru(CO)₃(L^1–4)₂]. The parent ligands and their complexes were characterized using elemental analyses and spectroscopic techniques. In addition, the structure of the representative ligand L¹ was determined using single‐crystal X‐ray analysis. The stereochemistry and theoretical optimization of the three‐dimensional geometry of the ligands and their complexes were justified. In vitro antimicrobial screening against bacterial stains Escherichia coli and Staphylococcus aureus and fungus Candida albicans was conducted. Cytotoxicity of the compounds as anti‐tumour agents was evaluated against liver carcinoma (HepG2), breast carcinoma (MCF7) and colon carcinoma (HCT‐116) cell lines relative to cisplatin and doxorubicin. The complexes showed variable in vitro cytotoxic activities against the three studied cell lines, with IC₅₀ values less than those of cis‐platin, and thus appear to be building blocks for promising anti‐tumour agents.     

Synthesis and characterization of diorganotin(IV) complexes of Schiff bases with ONO‐type donors and crystal structure of [N‐(2‐hydroxy‐4‐nitrophenyl)‐3‐ethoxysalicylideneiminato]diphenyltin(IV)

A series of neutral complexes, namely, [N‐(2‐hydroxy‐4‐nitrophenyl)‐3‐hydroxysalicylideneiminato]‐ diphenyltin(IV) ( Ia ), [N‐(2‐hydroxy‐4‐nitrophenyl)‐3‐methoxysalicylideneiminato]diphenyltin(IV) ( IIa ) and [N‐(2‐hydroxy‐4‐nitrophenyl)‐3‐ethoxysalicylideneiminato]diphenyltin(IV) ( IIIa ) were prepared by the reaction of diphenyltin dichloride on the corresponding Schiff bases. The Schiff bases were the reaction products of 2‐hydroxy‐4‐nitroaniline and appropriate salicylaldehydes. All the compounds were characterized by elemental analysis, ¹H‐NMR, ¹³C‐NMR, IR and mass spectroscopy. Compound IIIa was also characterized by single crystal X‐ray diffraction and shows a C₂NO₂ coordination geometry nearly half‐way between a trigonal bipyramidal and square pyramidal arrangement. In the solid state, π? π interactions exist between the aniline fragments of neighbouring molecules. Copyright © 2007 John Wiley & Sons, Ltd.     

Hafnium(IV) complexes with Schiff bases

Summary Hafnium(IV) complexes have been prepared by the reactions of hafnium(IV) isopropoxide isopropanol with Schiff bases [bis(salicylaldehyde)hydrazine] (Sal-AH₂), (bis(o-hydroxyacetophenone)hydrazine] (Acp-AH₂), [bis(resacetophenone)hydrazine] (Res-AH₂), [bis(salicylaldehyde)ethylenediimine) (SaleneH₂), [bis(o-hydroxyacetophenone)ethylenediimine] (AcpeneH₂) and [bis(salicylaldehyde)o-phenylenediimine] (SalpheneH₂) (derived from salicylaldehyde,o-hydroxyacetophenone, resacetophenone and diamines) in appropriate molar ratios using benzene as solvent. The complexes [Hf(OPr-i)₂(SB)] and [Hf(SB)₂] (where SB^2– represents the dianion of the Schiff base) are reported. The complexes of Sal-A, Acp-A and Res-A are 5-and 6-coordinate while those of salene, acpene and salphene are 6-and 8-coordinate. The Schiff bases draw on Sal-A, Acp-A and Res-A are tridentate and salene, acpene and salphene are tetradentate. The mode of bonding through nitrogen and oxygen and the stereochemistry of the complexes are discussed in relation to the elemental analyses and spectra (electronic, infrared and nuclear magnetic resonance).     

Erratum: Synthesis and characterization of diorganotin(IV) complexes of Schiff bases with ONO‐type donors and crystal structure of [N‐(2‐hydroxy‐4‐nitrophenyl)‐3‐ethoxysalicylideneiminato]diphenyltin(IV)

The article referenced above was first published online on 30 August 2007 with incorrect pagination; the pagination has now been corrected online and in print. Copyright © 2007 John Wiley & Sons, Ltd.