Chloro-diorganotin(IV) complexes of 4-methyl-1-piperidine carbodithioic acid: Synthesis, X-ray crystal structures, spectral properties and antimicrobial studies

Chloro-diorganotin(IV) complexes of 4-methyl-1-piperidine carbodithioic acid (4-MePCDTA) have been synthesized by the reaction with diorganotin dichloride in 1:1 molar ratio in anhydrous toluene. These newly synthesized complexes have been characterized by elemental, IR, multinuclear NMR (¹H and ¹³C) and mass spectrometric studies. The crystal structures of complex 1 [Me₂SnCl(4-MePCDT)] and 3 [Ph₂SnCl(4-MePCDT)] have been determined by X-ray single crystal analysis, which show trigonal bipyramid geometry. These complexes were tested for their antimicrobial activity against six different plant and human pathogens. The screening results show that the complexes exhibit higher antibacterial and antifungal activity than the free ligand.     

Monocyclopentadienyl titanium(IV) dithiocarbamate complexes

Preparation of titanium(IV) complexes of the type CpTi(dtc)Cl₂, CpTi(dtc)₂Cl and CpTi(dtc)₃ has been carried out by reacting CpTiCl₃ and respective sodium dithiocarbamate viz. N-(ethyl, m-tolyl), N-cyclopentyl and N-cycloheptyl dithiocarbamates in the desired metal to ligand ratio in refluxing dichlomethane. Studies of the physical properties reveal monomeric and nonelectrolytic nature of these complexes, where dithiocarbamate behaves as bidentate ligand. Therefore, 5, 6 and 7 coordinate structure can be assigned to CpTi(dtc)Cl₂, CpTi(dtc)₂Cl and CpTi(dtc)₃, respectively.     

Thermal and spectral studies of palladium(II) and platinum(IV) complexes with dithiocarbamate derivatives

Four new coordination complexes of palladium(II) and platinum(IV) starting from bis(dimethylthiocarbamoyl)sulphide (L¹) and bis(diethylthiocarbamoyl)disulphide (L²) were synthesized and characterized in solid state by elemental analysis, infrared and electronic spectroscopy as well as thermal analysis (TG/DTA). The complexes were formulated on the basis of experimental data as [Pd(Me₂NCS₂)₂] (1), [Pt(Me₂NCS)₂SCl₄]·3H₂O (2), [Pd(Et₂NCS₂)₂] (3) and [Pt(Et₂NCS)₂S₂Cl₄]·4H₂O (4), respectively. TG experiments revealed the nature of complex species as hydrated (2 and 4) or anhydrous (1 and 3). Thermal decomposition of coordinated organic ligands occurs in one or two exothermic stages, the final residue being in all cases the free metal (Pd or Pt).     

Local surrounding of cobalt(II) in dithiocarbamate complexes,their magnetic and spectral properties

[Co(S₂CNRR’)₂] complexes [R = R’ = CH₃, C₂H₅, C₃H₇, C₄H₉, or CH₂C₆H₅; RR’ = (CH₂)₅, (CH₂)₆, or (CH₂)₂O(CH₂)₂] were prepared via interaction of CoCl₂ with sodium dithiocarbamates in aqueous medium (pH 6–7). [Co(S₂CNRR’)₂] are low-spin compounds (μ_eff 2.19–2.45 μ_B) with distorted square-planar geometry of the CoS₄ coordination node. The Co-S bonds length is 2.22–2.26 Å, and the distance between cobalt and carbon atoms is 2.73–2.74 Å.     

Ruthenium(III) tetradentate Schiff-base complexes: spectral,catalytic, and its biocidal efficacy

New six-coordinate ruthenium(III) Schiff-base complexes of general formula [Ru(X)(PPh₃)(L)] (where X = Cl/Br and L = mononucleating bibasic tetradentate ligand derived by condensing actetoacetanilide/acetoacetotoludide with o-aminophenol/o-aminothiophenol/o-aminobenzoic acid in 1 : 2 molar ratio in ethanol) have been synthesized and characterized by physico-chemical and spectroscopic methods. The new ruthenium(III) complexes possess 2NO/2NS metal binding sites and are catalysts for the oxidation of alcohols using molecular oxygen as co-oxidant and in C–C coupling reactions. These complexes possess good biocidal (antibacterial and antifungal) activity.     

Syntheses,characterization, and antimicrobial properties of nickel(II) dithiocarbamate complexes containing NiS4 and NiS2PN moieties

Three Ni(II) dithiocarbamate complexes, [Ni(buphdtc)₂] (1), [Ni(buphdtc)(PPh₃)(NCS)] (2) and [Ni(buphdtc)(PPh₃)(NC)] (3) (where bu = butyl and ph = phenyl), were synthesized and characterized by elemental analysis, UVvis, and FTIR spectroscopies. Complexes 1 and 2 were further characterized by single-crystal X-ray structural analysis. The single-crystal X-ray structural analysis indicates a slightly distorted square planar geometry. In 2 and 3, the influences of the auxiliary ligands (PPh₃, NCS, and NC) on their steric and electronic properties were observed. Thermal studies of the complexes showed decomposition starting at 250–300 °C, leading to formation of nickel sulfide phases around 400 °C. The complexes were screened against some bacteria strains, Staphylococcus aureus, Streptococcus pneumoniae, Bacillus subtilis, Escherichia coli, Klebsiella oxytoca and Pseudomonas aeruginosa, and two fungi species, Aspergillus niger and Fusarium oxysporum. The complexes showed moderate-to-strong antimicrobial potentials, with [Ni(buphdtc)₂] (1) displaying the best antimicrobial activity. Fluconazole and streptomycin were used as reference drugs for antifungal and antibacterial assays, respectively.     

Diorganotin(IV) dithiocarbamate complexes as chromogenic sensors of anion binding

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.     

The preparation and characterization of new eight-coordinate vanadium(IV) dithiocarbamate complexes

The reaction between oxovanadium(IV) and the potassium salts of the four dithiocarbamates derived from indole, indoline, carbazole and pyrrole in a mixed acetonitrile-water solvent and subsequent recrystallization of the product gave pure VL₄ complexes. An IR, optical and electron spin resonance spectral characterization is reported. The data are consistant with a VS₈ chromophore with an approximate D_2d geometry.     

一些双(η^5-环戊二烯基)芳香酸钼(IV),钨(IV)配合物的合成和性质研究

本文报道了双(η^5-烷基环戊二烯基)水杨酸钼(IV),钨(IV),双(η^5-环戊二烯基)双(α-呋喃甲酸)钼(IV),钨(IV),双(η^5-环戊二烯基)双(取代苯甲酸)钼(IV),钨(IV)等三十四个配合物的合成及性质,这些配合物能同氯化氢,乙酰氯,二氯亚砜反应生成相应的二茂金属二氯化物,与氯化亚锡反应生成含有Mo-Sn键的配合物.通过对双(η^5-环戊二烯基)双(取代苯甲酸)钼(IV)配合物的^1^3C NMR谱考察,发现羧羰基碳的^1^3C化学位移值与取代基场效应常效(σ~I)有一直线关系.     

Syntheses and characterization of pentacoordinate organo-tin(IV) complexes II

Nine substituted benzoyl hydrazonyl, three semicarbazonyl, and four thiosemicarbazonyl tridentate ligands were synthesized. They were used to coordinate with Bu₂SnCl₂ or (PhCH₂)₂SnCl₂ to form 18 novel tin complexes that contained pentacoordinate organotin(IV) in a heterobicyclic ring. All these complexes were characterized by MS, NMR, and IR spectroscopy elemental analyses. © 1995 John Wiley & Sons, Inc.     

Thermochemical parameters of dimethyl and di-iso-propyl dithiocarbamate complexes of palladium(II)

The standard molar enthalpy of formation of crystalline dialkyldithiocarbamate chelates, [Pd(S₂CNR₂)₂], with R=CH₃ and i-C₃H₇, was determined through reaction-solution calorimetry in 1,2-dichloroethane, at 298 K. Using the standard molar enthalpies of formation of the gaseous chelates, the homolytic (526±18 and 666±10) and heterolytic (2693±18 and 2957±10 kJ mol^-1) mean enthalpies of palladium-sulphur bond dissociation were calculated. This revised version was published online in August 2006 with corrections to the Cover Date.     

Coordination chemistry of palladium(II) and platinum(II) complexes with bioactive Schiff bases: Synthetic,spectral, and biocidal aspects

The Schiff bases, 5-nitro-indol-2,3-dionehydrazinecarboxamide (HSCZ¹) and 7-nitro-indol-2,3- dionehydrazinecarboxamide (HSCZ²), have been synthesized by the condensation of 5-nitro-indol-2,3-dione and 7-nitro-1H-indol-2,3-dione with semicarbazide hydrochloride, respectively. The palladium(II) and platinum( II) complexes have been prepared by mixing palladium chloride and platinum chloride in 1: 2 molar ratios with monobasic bidentate Schiff bases. The ligands and complexes of palladium and platinum have been characterized by elemental analyses, melting point determinations, conductance measurements, molecular weight determinations, and IR, ¹H NMR, and UV spectral studies. These studies showed that the ligands coordinate to the metal atoms in a monobasic bidentate mode, coordinating through oxygen and nitrogen donor systems. Thus, a tetracoordinated environment around the metal atom has been proposed. Both the ligands and their complexes have been screened for their biological activity on several pathogenic fungi and bacteria and were found to possess appreciable fungicidal and bactericidal properties. Plant growth regulating activity of one of the ligands and its complexes has also been recorded on gram plant, and results have been discussed. The article is published in the original.     

Organotin(IV) complexes of thiohydrazides and thiodiamines: synthesis, spectral and thermal studies

Organotin(IV) complexes of tribenzyltin(IV) chloride and di(para-chlorobenzyl)tin(IV) dichloride with thiohydrazides have been reported. The ligands synthesized were bidentate coordinating through sulphur and terminal nitrogen atoms. These form 1:1 metal-ligand complexes. The following organotin(IV) complexes have been synthesized: (C(6)H(5)CH(2))(3)Sn(L(1))Cl, (p-ClC(6)H(4)CH(2))(2)Sn(L(1))Cl(2), (C(6)H(5)CH(2))(3)Sn(L(1))Cl, (p-ClC(6)H(4)CH(2))(2)Sn(L(2))Cl(2), (C(6)H(5)CH(2))(3)Sn(L(3))Cl, (p-ClC(6)H(4)CH(2))(2)Sn(L(3))Cl(2), where (L(1)): 2-phenylethyl N-thiohydrazide, (L(2)): N-(2-phenylethyl-N-thio)-1,3-propane diamine, (L(3)): N-(2-phenylethyl-N-thio)-1,2-ethane diamine. The complexes were synthesized by directly mixing, refluxing and stirring the ligands with organotin(IV) chlorides in a suitable solvent. The complexes were found to be pure and were characterized by elemental analysis, electronic, infrared, (1)H and (13)C NMR spectroscopy. These complexes were also studied for their thermal decomposition by thermogravimetry (TG) and differential thermal analysis (DTA). Various kinetic and thermodynamic parameters, viz. activation energy (E(a)), order of reaction (n), apparent activation entropy (S(#)) and heat of reaction (DeltaH) have been determined by using Horowitz-Metzger method. It was observed that these complexes are highly stable and the thermal degradation of these complexes is a spontaneous process. The ligands and their tin complexes have also been screened for their fungitoxicity activity and found to be quite active in this respect.     

Syntheses and characterization of doubly-bidentate bis(carboxyamide) complexes of oxomolybdenum(IV)

Summary Complexes of oxomolybdenum(IV) with doubly-bidentate bis(carboxyamide) ligands, derived by condensing benzidine (Bd) or p-phenylenediamine (PPD) with phthalic anhydride (PAH) and succinic anhydride (SAH), have been synthesized by phosphine oxo abstraction from dioxomolybdenum(VI) complexes via ligand displacement. The structures of the complexes were determined by elemental analyses, i.r. and electronic spectral data, cyclic voltammetry and thermal analysis.     

Synthesis,spectral, magnetic,and thermal properties of Ge(IV) tetrachlorocobaltates complexes with 2-hydroxyarylaldehydes pyridinoyl(aminobenzoyl) hydrazones

The interaction in the GeCl₄–nicotinoyl(isonicotinoyl, 2-, or 4-aminobenzoyl) hydrazone of 2-hydroxybenz(2-hydroxy-1-naphth)aldehyde (H₂L)–CoCl₂–methanol systems has resulted in the formation of [Ge(L·H)₂][CoCl₄]·nCH₃OH complexes with germanium chelates [Ge(L·H)₂]²⁺ protonated at the exo chelate nitrogen atom (N_Py or NH₂) as the cation. The type of electrolytic dissociation and character of thermolysis of the complexes have been revealed. Spectral, thermal, and magnetic properties of the complexes have been studied.     

Synthesis,spectral and biological studies of organotin(IV) complexes of heteroscorpionate

A heteroscorpionate ligand, potassium hydrobis(benzoato)(salicylaldehyde)borate (KL), has been synthesized. This was converted into organotin complexes R₂SnL₂ and R₃SnL complexes by mixing and stirring with a methanolic solution/suspension of organotin chloride. The ligand and its complexes were characterized by elemental analyses and spectral studies (IR, ¹H NMR, ¹³C NMR, ESI mass spectra and Thermo gravimetric analysis (TGA)). Antibacterial and antifungal studies of these compounds were evaluated by the disc diffusion method at variable concentration against three species of bacteria (Staphylococcus aureus, Klebsiella pneumonia and Bacillius subtillis) and two species of fungi (Asperjillius fiavus and Candida albicans). It was found that triorganotin derivatives (R₃SnL) of the ligand were more effective as compared with diorganotin derivatives (R₂SnL₂). The organotin complexes of borates were tested for their algicidal activity on the cyanobacterial strains Aulosira fertilissma, Anabaena species, Anabaena variabilis and Nostoc muscorum and showed high to moderate toxicity towards the above species. The ligand and its complexes were also tested for its pH effect on soil in vitro for a duration of more than one month and it was found that they are able to kill pests without damaging the soil quality. Copyright © 2006 John Wiley & Sons, Ltd.     

Synthesis,spectral characterization,crystal structures of lanthanide(III) pyrrolidine dithiocarbamate complexes and their catalytic activity

A series of lanthanide(III) pyrrolidine dithiocarbamate complexes [Ln(Pyrrol-Dtc)₃(Phen)] {Pyrrol-Dtc = pyrrolidine dithiocarbamate; Phen = 1,10-phenanthroline; Ln = La(III), Ce(III), Pr(III), Nd(III), Sm(III), Gd(III), Tb(III), Dy(III), Er(III)} have been synthesized and structurally characterized. The molecular structures of [La(Pyrrol-Dtc)₃(Phen)], [Pr(Pyrrol-Dtc)₃(Phen)], [Sm(Pyrrol-Dtc)₃(Phen)], and [Dy(Pyrrol-Dtc)₃(Phen)] have been confirmed using single crystal XRD studies. The results reveal that in these complexes, the central Ln(III) ion is coordinated to three Pyrrol-Dtc and one Phen and possesses a distorted dodecahedron geometry. Catalytic activity of these complexes in trimethylsilylcyanation reaction has been studied.     

Syntheses and reactivity of 'sulfur rich' Re(iii) and Tc(iii) complexes containing trithioperoxybenzoate, dithiobenzoate and dithiocarbamate ligands

Reduction-substitution reactions of [M(O)Cl(4)](-)(M=Re, (99)Tc) precursors with an excess of substituted dithiobenzoate ligands (R-PhCS(2))(-) in dichloromethane/methanol mixtures afford a series of six-coordinated neutral mixed-ligand complexes of the type M(III)(R-PhCS(3))(2)(R-PhCS(2))(M=Re; Rel--9; M=99)Tc; Tel--9). The coordination sphere is entirely filled by sulfur donor atoms, and the complexes adopt a distorted trigonal prismatic arrangement, as assessed by the X-ray crystal structure analysis of Re(4-Me-PhCS(3))(2)(4-Me-PhCS(2)), Re 2. These compounds show sharp proton and carbon NMR profiles, in agreement with the diamagnetism typical of low spin d(4) trigonal prismatic configurations. The red-ox processes involve reduction of the metal from Re(v) to Re(iii) and oxidation of dithiobenzoate to trithioperoxybenzoate. M2--9 complexes contain a substitution-inert [M(R-PhCS(3))(2)](+) moiety including the metal and two trithioperoxybenzoate fragments, while the third dithiobenzoate ligand is labile. The latter is efficiently replaced by reaction with better nucleophiles such as diethyldithiocarbamate giving a further class of mixed ligand complexes of the type M(III)(R-PhCS(3))(2)(Et(2)NCS(2))(M=Re; Re 10--18; M=(99)Tc; Tc--18), which retain the trigonal prismatic arrangement, as determined by the X-ray analyses of the representative compounds Re(PhCS(3))(2)(Et(2)NCS(2)), Re 10 and (99)Tc(PhCS(3))(2)(Et(2)NCS(2)), Tc 10.     

Schiff base supported mononuclear organotin(IV) complexes: Syntheses,structures and fluorescence cell imaging

Three mononuclear organotin(IV) complexes supported by Schiff bases have been synthesized. The complexes [(C₆H₅)₂Sn(L)] ( 1 ), [(t‐Bu)₂Sn(L)] ( 2 ) and [(t‐Bu)₂Sn(L')] ( 3 ) (L, L' = deprotonated Schiff bases) were obtained in good yield by the reaction of Schiff bases H ₂ L or H ₂ L′ with corresponding diorganotin dichlorides respectively. All newly synthesized complexes were characterized by means of FT‐IR spectroscopy, elemental analysis and multinuclear (¹H, ¹³C and ¹¹⁹Sn) NMR spectroscopy. In addition, single crystal X‐ray diffraction analyses were employed to establish the solid state molecular structures of these complexes. The structures of 1 – 3 reveal that all complexes are mononuclear with a five‐coordinated tin(IV) centre in it. The absorption and emission properties of all complexes have been investigated. Moreover, cytotoxicity and fluorescence cell imaging studies of theses complexes have been performed.