Synthesis,characterization, spectroscopic and catalytic oxidation studies of Fe(III), Ni(II), Co(III), V(IV) and U(VI) Schiff base complexes with N,O donor ligands derived from 2,3-diaminopyridine

Fifteen new complexes of transition metals were designed using three Schiff base ligands and aldol condensation of 2,3-diaminopyridine with 5-R-2-hydroxybenzaldehyde (R = F, Cl, Br) in the 1:2 molar ratio. The tetradentate ligands N,N′-bis(5-R-2-hydroxybenzaldehyde) pyridine were acquired with the common formula H₂[(5-R-sal)₂py] and characterized by IR, UV–Vis spectra, ¹H-NMR and elemental analysis. These ligands produce 1:1 complexes M[(5-R-sal)₂py] with Fe(III), Ni(II), Co(III), V(IV) and U(VI) metal ions. The electronic property and nature of complexes were identified by IR, UV–Vis spectra, elemental analysis, X-ray crystallography and cyclic voltammetric methods. The catalytic activity of complexes for epoxidation of styrene with UHP as primary oxidant at minimal temperature (10 °C) has been planned. The spectral data of the ligands and their complexes are deliberate in connection with the structural changes which happen due to complex preparation. The electrochemical outcome has good conformability with what suggested for electronic interaction among metal center and ligand by the UV–Vis and IR measurements.     

Mn(II), Co(II), Ni(II) and Cu(II) complexes of a tertraaza macrocyclic ligand: Synthesis, characterization and biological screening

Manganese(II), cobalt(II), nickel(II) and copper(II) complexes with 1,5,11,15-tetraaza-21,22-dioxo-tricyclo [19,3,1,I^6,10]-5,10,15-20-dicosatetraene (L), as a new macrocyclicligand, have been synthesized with and characterized by elemental analysis, molar conductance measurements, magnetic susceptibility measurements, mass, IR, electronic and EPR spectral studies. The molar conductance measurements of the complexes in DMF correspond to non-electrolytic nature of Mn(II), Co(II) and Cu(II) complexes, while showing a 1:2 electrolyte for thew Ni(II) complexe. Thus, these complexes may be formulated as [M(L)X₂] and [Ni(L)]X₂ (where M = Mn(II), Co(II) and Cu(II) and X = Cl^- and NO₃ ^-). On the basis of IR, electronic and EPR spectral studies, an octahedral geometry has been assigned for Mn(II) and Co(II), a square planar for Ni(II) and tetragonal for Cu(II) complexes. In vitro ligand and its metal complexes were also screened against the growth of some fungal and bacterial species in order to assess their antimicrobial properties.     

Syntheses,Spectral, and Biological Studies of New Imines Derived From 5-Bromothiophene-2-Carboxaldehyde and Their Si(IV), Sn(IV) Complexes

The Schiff bases (imines) HL¹ and HL² have been synthesized by the reaction of 5-bromothiophene-2-carboxaldehyde with 4-amino-5-mercapto-1,2,4-triazole and 4-amino-3-ethyl-5-mercapto-1,2,4-triazole, respectively. Organosilicon(IV) and organotin(IV) complexes having the general formulae R₂MCl(L¹), R₂MCl(L²), R₂M(L¹)₂, R₂M(L²)₂, (M = Si, Sn; R = CH₃) were synthesized by the reaction of R₂MCl₂ with these Schiff bases in 1:1 and 1:2 molar ratio. The Schiff bases and their metal complexes have been characterized with the aid of elemental analyses, molar conductance, and spectroscopic studies, including UV, IR, ¹H, ¹³C, MS, ²⁹Si, and ¹¹⁹Sn NMR spectroscopy. On the basis of these studies, the resulting complexes have been proposed to have trigonal bipyramidal and octahedral geometries. In vitro activities of the Schiff bases and their metal complexes against some Gram positive and Gram negative bacteria and fungi have been carried out and described.     

Synthesis,spectroscopic, antibacterial and antifungal studies of nickel(II)5(2′-hydroxyphenyl)-3-(4-X-phenyl)pyrazolinates and their addition complexes with N and P donor ligands

A number of complexes of nickel(II) with 5(2′-hydroxyphenyl)-3-(4-X-phenyl)pyrazolines of the type (C₁₅H₁₂N₂O ··· X)₂Ni [where X = H, Cl, CH₃ and OCH₃] were synthesized by the reaction of anhydrous nickel(II) chloride with sodium salts of pyrazoline in 1 : 2 molar ratio. Their addition complexes with 2,2′-bipyridine, 1,10-phenanthroline and triphenylphosphine were prepared in 1 : 1 molar ratio. These complexes were characterized by elemental analyses, molecular weight, magnetic, conductivity, IR, electronic, ¹H, ¹³C, ³¹P NMR and FAB mass spectral data. All complexes are amorphous. Square planar geometry around nickel confirms the presence of two bidentate pyrazoline ligands in nickel(II)5(2′-hydroxyphenyl)-3-(4-X-phenyl)pyrazolinates. In the addition complexes pyrazoline is monodentate. Bidentate and monodentate pyrazoline was confirmed by IR, ¹H, ¹³C and ³¹P NMR spectral data. All the metal complexes exhibit very good antibacterial and antifungal activity. Coordination of metal ion has pronounced effect on the microbial activities of the ligand. The brine shrimp bioassay was also carried out to study their in vitro cytotoxic properties; all complexes and adducts display potent cytotoxic activity against Artemia salina.     

Syntheses,spectral characterization,thermal properties and DNA cleavage studies of a series of Co(II), Ni(II) and Cu(II) polypyridine complexes with some new imidazole derivatives of 1,10-phenanthroline

In the present study three new imidazole derivatives of phen, 2-(4-hydroxy-3,5-diiodophenyl) imidazo[4,5-f][1,10]phenanthroline L¹, 2-(2-hydroxy-3,5-diiodophenyl)imidazo[4,5-f][1,10]phenanthroline L², 2-(4-hydroxy-5-iodo-3-methoxyphenyl)imidazo[4,5-f][1,10]phenanthroline L³ and their nine new polypyridine complexes[M(N–N)₂(L^1–3)](OAc)₂·(nH₂O) where M is Ni(II), Co(II) and Cu(II) and where (N–N)₂ is 2,2′-bipyridine (bpy)₂ or 1,10-phenanthroline (phen)₂ have been synthesized from the reaction of the metal precursor complexes [M(phen)₂(OAc)₂]·(nH₂O) and [M(bpy)₂(OAc)₂]·(nH₂O) with the respective ligands in ethanol and water. The structures of the compounds were determined with the aid of elemental analysis and FT-IR, UV–Vis, ¹H NMR, ESR spectroscopic methods, magnetic measurements and conductance measurements, further analyzed by powder XRD and thermal studies. Elemental analysis data suggested that the complexes have a 1:2:1 molar ratio among the metal and phen or bpy and L¹/L² or L³ ligands. The spectral data show that all the complexes were six coordinated and possess octahedral geometry around the metal ions. The X-band ESR spectrum of the Cu(II) in DMSO solution at room temperature was recorded and observed anisotropic g values indicate the presence of metal ion in an octahedral environment. The powder XRD patterns of complexes recorded in the range (2θ = 0–80°) and average crystallite size (d_XRD) was calculated using Scherrer’s formula. Thermal decomposition profiles of complexes show high decompound temperatures indicating a good thermal stability. Binding of the complexes with calf thymus DNA (CT DNA) has been investigated by gel electrophoresis. The experimental results indicate that the complexes bind to DNA by intercalation mode and found to promote cleavage of plasmid pBR 322 DNA from the supercoiled form I to the open circular form II upon irradiation.     

Vanadium complexes with quadridentate Schiff bases

The Schiff base ligands N,N′-(±)-trans-bis(3,5-dichloro-2-hydroxyacetophenone)-1,2-cyclohexanediamine (H₂L¹) and N,N′-(±)-trans-bis(5-chloro-4-methyl-2-hydroxyacetophenone)-1,2-cyclohexanediamine (H₂L²) were derived from the condensation of trans-1,2-diaminocyclohexane with 3,5-dichloro-2-hydroxyacetophenone or 5-chloro-4-methyl-2-hydroxyacetophenone, respectively. Both these ligands formed well-defined complexes with vanadium (IV) and (V) under suitable experimental conditions. These complexes have been characterized by elemental analysis, molar conductivity, magnetic moments, infrared, electronic spectra, ESR, X-ray diffraction, and thermogravimetric analysis. X-ray diffraction study of [VO(L²)]·H₂O complex indicated its monoclinic crystal system with a = 9.8525, b = 23.6271, c = 9.0904 Å, and β = 97.87°. The complexes [VO(L¹)]·H₂O and [VO(L²)]·H₂O have been examined as catalysts for epoxidation of styrene in the presence of hydrogen peroxide as oxidant. The IR spectral data suggest that both the ligands behave as dibasic tetradentate chelating agent with ONNO donor atoms sequence toward cental metal ion.     

Dinuclear peroxo complexes of molybdenum(VI) containing Mannich base ligands

Dinuclear molybdenum(VI) peroxo complexes containing Mannich base ligands having formulae [Mo₂O₄(O₂)₂L-L(H₂O)₂] · H₂O [where L-L = N-[1-morpholinobenzyl] acetamide (MBA), N-[1-piperidinobenzyl] acetamide (PBA), N-[1-morpholino(-4-nitrobenzyl)] benzamide (MPNBB), N-[1-piperidino(-3-nitrobenzyl)] benzamide (PMNBB), N-[1-morpholino(-2-nitrobenzyl)] acetamide (MONBA), and N-[1-morpholino(-3-nitrobenzyl)] acetamide (MMNBA)] have been synthesized by stirring ammonium heptamolybdate with excess 30% aqueous hydrogen peroxide followed by treatment with ethanolic solution of corresponding ligands. The complexes have been characterized by elemental analysis, molar conductance, magnetic measurements, infrared (IR), electronic, TGA/DTA, mass spectral, and ¹H NMR studies. The complexes are non-electrolytes and diamagnetic. The IR spectral studies suggest that the ligands are bidentate to metal through carbonyl oxygen and ring nitrogen. Thermal analyses provide conclusive evidence for the presence of coordinated, as well as lattice water in the complexes. Dinuclear complexes preserve the individuality of the molybdenum oxo peroxo core. The complexes exhibit higher antibacterial activity against bacterium Ralastonia solanacearum (Pseudomonas solanacearum) than the free ligands.     

Synthesis, thermal characterization, and antimicrobial activity of lanthanum, cerium, and thorium complexes of amino acid Schiff base ligand

Metal complexes of La(III), Ce(IV), and Th(IV), with the amino Schiff base ligand, [N-(2-hydroxybenzyl)-l-methionine acid](H₃L), were prepared in the presence of triethylamine as a deprotonating agent. All synthesized compounds were identified and confirmed by mass spectra, elemental analyses, molar conductivities, and spectral analyses (UV–Visible, IR, ¹H NMR, and ¹³CNMR). Conductance measurements suggest the non-electrolytic nature and the complexes were isolated in 1:1 ratios. The thermal decomposition of the complexes was discussed in relation to structure. The data from thermogravimetric analysis clearly indicated that the decomposition of the complexes proceeds in four or five steps and the organic part of the complexes decomposed in one or two intermediates. The decomposition of all complexes ended with metal oxide and carbon residue. The Schiff bases and their complexes were screened for their antibacterial (Escherichia coli, Staphylococcus aureus) and antifungal (Aspergillus flavus and Candida Albicans) activities.     

A novel vic-dioxime ligand and its Ni(II), Cu(II) and Co(II) complexes containing calix[4]pyrrole moiety: synthesis, characterization and redox properties

A new calix[4]pyrrole functionalized vic-dioxime, 3-(4-methyl-9,9,14,14,19,19-hexaethylcalix[4]pyrrole)benzoaminoglyoxime (LH₂) was synthesized from anti-chloroglyoxime and 3-aminophenyl-calix[4]pyrrole at room temperature. The mononuclear complexes {nickel(II), copper(II) and cobalt(II)} of this vic-dioxime ligand were prepared and their structures were confirmed by elemental analysis, IR and UV–Vis spectrophotometry, magnetic susceptibility; the MS, ¹H and ¹³C NMR spectra of the LH₂ ligand and its Ni(II) complex were also recorded. The experimental results indicated that the ligand:metal ratio was 2:1 in the cases of Ni(II), Cu(II) and Co(II) complexes as is with most vic-dioximes. Electrochemical properties of the ligand, and its complexes were investigated in DMSO solution by cyclic voltammetry at 200?mV?s^?1 scan rate.     

Synthesis and characterization of novel (<Emphasis Type="Italic">E</Emphasis>,<Emphasis Type="Italic">E</Emphasis>)-dioxime and its mono- and polynuclear metal complexes containing azacrown moieties

The novel (E,E)-dioxime,7,8-bis(hydroxyimino)-1,14-bis(monoaza[8]crown-6)-benzo[f]-4,11-dioxa-1,14-diazadecane[7,8-g]quinoxaline (H₂L), has been synthesized by the reaction of 6,7-diamino-1,12-bis(monoaza[18]crown-6)benzo[f]-4,9-dioxa-1,12-diazadecane (4) which has been prepared by the reduction of 6,7-dinitro-1,12-bis(mono-aza[18]crown-6)benzo[f]-4,9-dioxa-1,12-diazdecane (3) and cyanogendi-N-oxide. Mononuclear Ni^II and Cu^II complexes of H₂L have a metal:ligand ratio of 1:2 and the ligand coordinates through two hydroxyimino nitrogen atoms, as do most of the (E,E)-dioximes. The hydrogen-bridged Ni^II complex was converted into its BF ₂ ⁺ capped anologue by the reaction with BF₃ · Et₂O. The reaction of the Cu^II complex with 2,2′-dipyridyl as an end-cap ligand gave the homotrinuclear complex. Structures for the ligand and its complexes are proposed in accordance with elemental analysis, magnetic susceptibility measurements, ¹H, ¹³C-n.m.r, IR and MS spectral data.     

Lanthanide complexes derived from hexadentate macrocyclic ligand: Synthesis,spectroscopic and thermal investigation

The lanthanide complexes derived from (3,5,13,15-tetramethyl 2,6,12,16,21-22-hexaazatricyclo[15.3.I^1-17I^7-11]cosa-1(21),2,5,7,9,11(22),12,15,17,19-decane) were synthesized. The complexes were found to have general composition [Ln(L)X₂·H₂O]X, where Ln = La³⁺, Ce³⁺, Nd³⁺, Sm³⁺ and Eu³⁺ and X = NO₃^? and Cl^?. The ligand was characterized by elemental analyses, IR, Mass, and ¹H NMR spectral studies. All the complexes were characterized by elemental analyses, molar conductance measurements, magnetic susceptibility measurements, IR, Mass, electronic spectral techniques and thermal studies. The ligand acts as a hexadentate and coordinates through four nitrogen atoms of azomethine groups and two nitrogen of pyridine ring. The lanthanum complexes are diamagnetic while the other Ln(III) complexes are paramagnetic. The spectral parameters i.e. nephelauxetic ratio (β), covalency factor (b^1/2), Sinha parameter (δ%) and covalency angular overlap parameter (η) have been calculated from absorption spectra of Nd(III) and Sm(III) complexes. These parameters suggest the metal–ligand covalent bonding. In the present study, the complexes were found to have coordination number nine.     

Iron(III)5(2′-hydroxyphenyl)-3-(4-X-phenyl)pyrazolinates and their addition complexes with N,P donor ligands: synthesis,spectral and antimicrobial investigations

Iron(III)5(2′-hydroxyphenyl)-3-(4-X-phenyl)pyrazolinates of the type (C₁₅H₁₂N₂OX)₃Fe [where X =–H,–Cl,–CH₃,–OCH₃] have been synthesized by reaction of anhydrous FeCl₃ with the sodium salts of pyrazoline in 1 : 3 molar ratio. Their addition complexes with N and P donor ligands [2,2′-bipyridine, 1,10-phenanthroline and triphenylphosphine] were prepared in 1:1 molar ratio. These newly synthesized derivatives have been characterized using elemental analysis (C, H, N and Fe), molecular weight measurement, magnetic moment data, FAB mass, ³¹P NMR and Mössbauer spectral data. The complexes have been examined for crystalline/amorphous nature through XRD; all complexes are amorphous. Octahedral geometry around iron(III) confirms the presence of three bidentate pyrazoline ligands in iron(III)5(2′-hydroxyphenyl)-3-(4-X-phenyl)pyrazolinates. In addition complexes pyrazoline is monodentate. The bidentate and monodentate behavior of pyrazoline ligands was confirmed by IR spectral data. All the complexes were tested for their in-vitro antimicrobial activity. The metal complexes and their adducts exhibit better antibacterial and antifungal activity than the pyrazolines.     

Coordination behaviour in transition metal complexes of asymmetric NPN ligands

Two bicyclic, chiral aminophosphine ligands, namely 4R, 9R-1,3-bis(pyridin-2-ylmethyl)-2-(2-propyl)octahydro-1H-1,3,2-benzodiazaphosphole (1) and 4R, 9R-1,3-bis(pyridin-2-ylmethyl)-2-(2-ethoxy)octahydro-1H-1,3,2-benzodiazaphosphole (2) have been prepared from 1R, 2R-diaminocyclohexane and the appropriate dichlorophosphine and the nature of their coordination to a number of transition metals explored. Ligand 1 coordinates to Pd(II) and Pt(II) as a terdentate donor to give complexes of the type [M(κ³-N,P,N-1)Cl]⁺ whereas ligand 2 favours bidentate κ²-P,N coordination to give the complexes M(κ²-P,N-2)Cl₂. The study of the coordination chemistry of the NPN ligand 1 is frustrated by its ready decomposition to an unknown species which appears to be promoted by transition metals. The ligand 2 does not undergo such a transformation and its metal chemistry is more readily examined. Aside from the Pt(II) and Pd(II) complexes above, 2 has been coordinated to Cr(0) and Mo(0) in the octahedral complexes M(κ²-P,N-2)(CO)₄ and Au(I) in linear Au(κ¹-P-2)Cl. All the complexes have been fully characterised by spectroscopic and analytical techniques including a single-crystal X-ray structure analysis of [Pt(κ³-N,P,N-1)Cl]Cl, 3.     

Spectroscopic validation and biological screening of new iron(III) complexes with N,O donor ligands

Monometallic trivalent complexes of iron were synthesized by reaction between N, O type donor ligands (L) or (L′) and metal salt in a 1:2 (metal:ligand) molar ratio. Structure and composition of metal complexes were evaluated by elemental analysis, conductance measurements, magnetic moment measurements, and various spectroscopic studies viz. FTIR, UV–visible, and ESI–MS. Analytical and molar conductance data are consistent with the formulation of complexes as [Fe(L)₂X₂]·X and [Fe(L′)₂X₂]·X (where; L = Hydrazine carboxylic acid ethyl ester, L′ = Hydrazine carboxylic acid tert-butyl ester and X = Cl^?, Br^? or NO₃ ^?) due to their 1:1 electrolytic nature. IR spectral data revealed bi-dentate coordination behavior of ligands. An octahedral geometry may be assigned for metal complexes on the basis of electronic absorption data and magnetic moment parameters. The compounds were evaluated for their biological activity by in vitro antimicrobial screening against bacteria Staphylococcus aureus, Bacillus subtilis, Escherichia coli, and Salmonella typhi and fungi Candida parapsilosis and Saccharomyces cerevisiae. The results indicate that metal complexes exhibit more activity than free ligands against studied microbes.     

Efficient enantiorecognition of ruthenium(II) complexes by silica-bound teicoplanin

A series of chiral tris-diimine ruthenium(II) complexes have been resolved by HPLC on a chiral stationary phase. The stationary phase (CSP1) was prepared by covalent attachment of the glycopeptide antibiotic teicoplanin to isocyanate activated silica gel. CSP1 selectively retains the enantiomers of [Ru(L)₃]²⁺ (L=2,2′-bypyridine (bpy), 1,10-phenanthroline and 4,7-diphenyl-1,10-phenanthroline), with a preference for the Δ isomer. For the mixed-ligand complexes [Ru(bpy)₂pztr]⁺ and [Ru(bpy)₂pytr]⁺ (Hpztr=3-(pyrazin-2-yl)-1,2,4-triazole, Hpytr=3-(pyridin-2-yl)-1,2,4-triazole), where the triazole unit is bound to the metal centre either through the N² or the N⁴ nitrogen of the ring, CSP1 discriminates both the enantiomers and the regioisomers. Diastereo- and enantioselective association was also observed between CSP1 and the stereoisomers of the dinuclear complex ((Ru(bpy)₂)₂bpt]³⁺ (Hbpt=3,5-bis(pyridin-2-yl)-1,2,4-triazole), with differences in binding affinities of 1.4 kJ/mol between the homochiral enantiomers.     

微波促进下3-(2-苯并呋喃基)-4-氨基-5-巯基-1,2,4-三唑

微波辐射条件下, 首先由2-苯并呋喃甲酰肼依次与二硫化碳和水合肼反应合成3-(2-苯并呋喃基)-4-氨基-5-巯基- 1,2,4-三唑, 进一步在微波辐射条件下由4-氨基-5-巯基-1,2,4-三唑分别与芳甲酸/芳氧基乙酸、α-溴代苯乙酮及芳醛反应以较高产率制得了相应的1,2,4-三唑并[3,4-b]-1,3,4-噻二唑、1,2,4-三唑并[3,4-b]-1,3,4-噻二嗪及4-芳亚甲基亚胺基-5-巯基-1,2,4-三唑. 产物结构经IR, ¹H NMR, MS及元素分析进行了表征.     

A convenient,rapid microwave assisted synthesis of some novel 3-[(4-chloro-3-methylphenoxy)methyl]-6-aryl-5,6-dihydro-[1,2,4]triazolo[3,4-b][1,3,4]thiadiazoles using acidic alumina

A facile synthesis of 3-[(4-chloro-3-methylphenoxy)methyl]-6-aryl-5,6-dihydro-[1,2,4]triazolo[3,4-b][1,3,4]thiadiazoles 3a–n has been achieved by microwave promoted condensation of 3-mercapto-4-amino-5-[(4-chloro-3-methylphenoxy)methyl]-4H-1,2,4-triazole 1 with various aromatic aldehydes 2a–n in presence of catalytic amount of p-TsOH (para-toluenesulphonic acid). The structures of 3a–n are supported by IR and ¹H and ¹³C NMR spectral data.     

Synthesis,Spectroscopic Characterization,and Antifungal Activity of Some Mixed Ligand Complexes of Zn(II), Cd(II), and Hg(II)

A series of new mixed ligand complexes of Zn(II), Cd(II), and Hg(II) with citronellal thiosemicarbazone [3,7-dimethyl-6-octene-1-a1 thiosemicarbazone (LH)] and N-phthaloyl amino acids (AH) have been synthesized by the reaction of metal(II) chloride with ligands citronellal thiosemicarbazone (DOTSC) and N-phthaloyl glycine [1,3-dihydro-1,3-dioxo-2H-isoindole-2-acetic acid (A₁H)] or N-phthaloyl alanine [1,3-dihydro-1,3-dioxo-α(methyl)-2H-isoindole-2-acetic acid (A₂H)] in 1:1:1 molar ratio in dry refluxing ethanol. All the complexes have been characterized by elemental analyses, molar conductance measurement, molecular weight measurement, IR, and multinuclear NMR (¹H and ¹³C{¹H}) spectral studies. IR, ¹H, and ¹³C{¹H} NMR spectral studies suggest the involvement of azomethine-N, thiol-S atoms of the thiosemicarbazone moiety and both carboxylate-O of N-phthaloyl amino acid moiety in coordination with central metal(II) ion, and four coordinated geometries have been assigned to these complexes. The free ligands and metal complexes have been screened for their antifungal activity against two fungal strains, Fusarium moniliformae and Macrophomina phaseolina, using the the radial growth method. The results of antifungal activity show that metal complexes show enhanced higher activity than the free ligands.

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.     

The photochemical synthesis of novel heterocyclic compounds from s-triazolo [4,3-b] pyridazine,III

s-Triazolo[4,3-b]pyridazine (I) reacted photochemieally with bieyélo[2.2.1] hepla-2,5-diene, 1,5-cyclooctadiene, 1,3-cyclooctadiene, methylene cyclohexane, diethyl cis-1,2,3,6-tetrahydro-phthalate and ethyl 2-cyclopentene-1-acetate to givt: the following products: the endo and exo isomers of 4a, 5, 8a, 9-tetrahydro-9-rnethylene-5,8-rnethano-8H-s-triuzolo[1, 5-a]indole (II) and the endo and exo-9-cyanometliyl products (III and IV) from bicyclo[2.2.1] hepta-2,5-diene; 4a,5,-9, 10, 10a, 11-huxahydro-11-methylene-6H-cycloocta[4,5]pyrrolo[1,2-b]-s-triazole (V) and the 11-cyanomethyl product VI from 1,5-cyclooctadiene: 4a,7,8,9,10,10a-hexahydro-11 -inethylene-11H-cycloocta[4,5]pyrrolo[1,2-b]-s-triazole(VII),4a, 5, 7, 8, 10a, 11-hexahydro-11-methylene-6H-cycloocta[4,5]pyrroIo[1,2-b]-s-triazole (VIII) and their respective 9-cyanomethyl products (X and 1X) from 1,3-cyclooctadiene; 6′, 7′ -dihydro-7′ -methylenespiro[cyclohexane-1, 5′-[5H] pyr-rolo[1,2-b]-s-triazole] (XI), 6′, 7′-dihydro-7′-meth) lene. spiro cyclohexane-1, 6′-[5H]pyrrolo[1,2-b]-s-triazole] (XII) and their respective 7 -eyanomethyl products (XIII and XIV) from melhylene cyclohexane; 6,7-dicarbethoxy-9-cyanomelhyl-4a, 5, 7, 8, 8a, 9-hexahydro-6H-s-triazolo[1,5-a]indole (XV) from diethyl cis-1, 2, 3, 6-tetrahydrophlhalate: and 5-earl)elhoxymethyl-8-eyanomethyl-4a, 5, 6, 7, 7a, 8-hexahydrocyclopenta[4,5]pyrrolo( 1, 2-b]-s-triazole (XVI) from ethyl 2, 2-cyclo-pentene-1-acetate. Many other alkenes, particularly the phenyl ethylenes, did not react with compound 1. In general, more than one product was isolated for each reaction except in the case of the two ester alkenes where a single eyanomethyl product was observed.     

Synthesis and characterization of Hg(II) and Zn(II) complexes based on 3-[(4-chlorophenylamido)]propenoic acid

3-[(4-Chlorophenylamido)]propenoic acid has been synthesized by reaction of maleic anhydride and 4-chloroaniline in 1:1 molar ratio in glacial acetic acid and its metal complexes have been synthesized by the reaction of 3-[(4-chlorophenylamido)]propenoic acid with HgCl₂ and [Zn(CH₃COO)₂] · 2H₂O in 2: 1 molar ratio, respectively. All the synthesized compounds have been characterized by the elemental analysis, IR, UV/Vis and NMR (¹H, ¹³C) spectroscopy. Conductance for the reported compounds has been recorded in ethanol and suggests the non-electro lytic nature of complexes. IR data of metal complexes shows that the ligand is bound to the metal via both carboxylate oxygen atoms and complexes exhibits 4-coordinated geometry in solid state. NMR (¹H, ¹³C) study confirms the structure of the 3-[(4-chlorophenylamido)]propenoic acid and the reported complexes.