Synthesis of nickel(II)-di(2,3-dichlorophenyl)carbazonate and its adduct formation with heterocyclic nitrogen bases

The nickel(II)-di(2,3-dichlorophenyl)carbazonate [Ni(D2,3DClPC)₂] complex has been prepared and characterized by elemental and spectral studies. The Ni^II chelate forms adducts with heterocyclic nitrogen bases, which were studied spectrophotometrically in monophase CHCl₃ media. Saturated monodentate bases such as pyrrolidine, piperidine, etc., form pentacoordinate adducts of 1:1 stoichiometry, whereas bidentate and unsaturated monodentate bases form hexacoordinated adducts with 1:1 and 1:2 metal–ligand stoichiometries respectively. The results are discussed interms of steric properties, basicity and ring structures of the heterocyclic bases.     

Heterocyclic nitrogen base adducts of nickel(II)–di(2,4-dibromophenyl)carbazonate

The title complex was prepared and characterized by elemental and spectral analyses. The formation constants of various heterocyclic nitrogen base adducts with the Ni^II–di(2,4-dibromophenyl)carbazonate have been determined in a monophase by spectrophotometry at 25 ± 0.1 °C. The monodenatate and bidentate bases form penta- and hexa-coordinated adducts respectively with 1:1 stoichiometry for the metal chelate-base, whereas the unsaturated monodentate bases form hexa-coordinated adducts with 1:2 stoichiometry. The behaviour of saturated heterocyclic bases such as pyrrolidine, piperidine, hexamethyleneimine and morpholine towards the metal chelate has been studied, and the results are discussed in terms of steric hindrance, basicity and ring structure.     

A study of adduct formation of heterocyclic nitrogen bases with nickel(II) chelate of di(6-chloro-2-methylphenyl)carbazone

The study of the adduct formation of Ni(II) di(6-chloro,2-methylphenyl)carbazonate has been undertaken by synthesising and characterizing it by magnetic susceptibility, UV-VIS, IR and 1H-NMR spectral measurements. The distorted square planar Ni(II) chelate forms adducts with heterocyclic nitrogen bases; spectrophotometric method has been employed for the study of the adduct formation in a monophase chloroform. Both bidentate and unsaturated monodentate heteronuclear nitrogen bases form hexacoordinated adducts with 1:1 and 1:2 stoichiometry, respectively (metalchelate:base). However, the saturated nitrogen bases form pentacoordinated adducts with 1:1 stoichiometry. The results are discussed in terms of basicity and steric factors of the bases.     

Spectrophotometric study on the adduct formation of nickel (II)-di(2,4-dimethylphenyl)carbazonate with heterocyclic nitrogen bases

The study of the adduct formation of Ni(II)di(2,4-dimethylphenyl)cabazonate has been undertaken by synthesising and characterising it by magnetic susceptibility, IR and 1H-NMR spectral measurements. The Ni(II) chelate forms adducts with heterocyclic nitrogen bases, spectrophotometeric method has been employed for the study of the adduct formation in a monophase chloroform. Both bidentate and unsaturated monodenate heteronuclear nitrogen bases form hexa-coordinated adducts with 1:1 stoichiomety (metal chelate, base). However, the saturated nitrogen bases form penta-coordinated adducts with 1:1 stoichiometry. The results are discussed in terms of basicity and steric factors of the bases.     

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.     

Synthesis of nickel(II)-di(5-chloro-2-methylphenyl)carbazonate and its adduct formation with heterocyclic nitrogen bases

Summary The title complex has been synthesized and characterized by elemental and spectral analysis. The Ni^II chelate forms adducts with heterocyclic nitrogen bases, which were characterized spectrophotometrically in solution. Bidentate and unsaturated monodentate bases form hexacoordinate adducts with 11 and 12 metalligand stoichiometries, respectively, whilst saturated nitrogen bases form pentacoordinate adducts with 11 stoichiometry. The results are discussed in terms of basicities and steric properties of the bases.     

Struktur-Reaktivitäts-Beziehungen bei koordinativ ungesättigten Chelatkomplexen. III. Vergleich des Akzeptorverhaltens der Nickel- und Cobalt(II)-Chelate von dreizähnigen,dianionischen Schiffschen Basen

Structure Reactivity Relations of Coordinatively Unsaturated Chelate Complexes. III. Acceptor Tendency of Nickel and Cobalt Chelates with Tridentate Di-anionic Schiff Base Ligands The reactivity of nickel and cobalt chelate complexes of the type 3 with several donors is compared by isolation of stable adducts. In the case of nickel the reactivity is vigorously influenced by the substituents R¹ and R². The equatorial and the axial unoccupied coordination centers of the nickel chelates exhibit a markedly different behaviour. The cobalt(II) chelates – all of them are high spin complexes – favour O-donors. The complicate composition of the adducts point to a polynuclear structure. With pyridine, high spin diadducts have been isolated probably with coordination number 5 for the metal.     

Synthesis,spectral and biological investigations of 5(2′-hydroxyphenyl)-3-(4-substituted-phenyl) pyrazolinates of cobalt(II) and their addition complexes with N,P donor ligands

5(2′-Hydroxyphenyl)-3-(4-substituted-phenyl)pyrazolinates of cobalt(II) of the type (C₁₅H₁₂N₂OX)₂Co [here substituted group X is–H,–Cl,–CH₃ or–OCH₃] have been synthesized by reaction of anhydrous cobalt(II)chloride with the sodium salt of the pyrazolines in 1 : 2 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. The newly synthesized complexes were characterized by elemental analyses, molecular weight measurement, magnetic susceptibility, IR, electronic, ³¹P NMR and FAB mass spectra. All complexes are amorphous as determined by XRD. Tetrahedral geometry around cobalt(II) has been suggested, confirming the presence of two pyrazoline bidentate ligands, cobalt(II)5- (2′-hydroxyphenyl)-3-(4-substituted-phenyl)pyrazolinates. Upon ligand addition, pyrazoline changes to monodentate. The bidentate and monodentate behavior of pyrazoline ligands was confirmed by IR spectral data. The metal complexes and their adducts exhibit good antibacterial and antifungal activity, better than the pyrazolines.     

Synthesis,structural characterization,and anti-ulcerogenic activity of schiff base ligands derived from tryptamine and 5-chloro, 5-nitro, 3,5-ditertiarybutyl salicylaldehyde and their nickel(II), copper(II), and zinc(II) complexes

Ni(II), Cu(II), and Zn(II) complexes with bidentate Schiff bases derived from the condensation reaction of 5-chlorosalicylaldehyde, 5-nitrosalicylaldehyde, and 3,5 ditertiarybutyl-2-hydroxy benzaldehyde with tryptamine, have been reported. The ligands and complexes were characterized by elemental analysis, IR, ¹H NMR and UV–Vis spectroscopy as well as single crystal X-ray structure analysis whenever possible. The complexes were found to have the general formula [M(L)₂]. Spectral studies reveal that these Schiff bases were acting as bidentate ligands and co-ordinating to the metal center through deprotonated phenolate oxygen and azomethine nitrogen atoms. The Zn(II) complexes establish a tetrahedral geometry in a 1:2 metal to ligand stoichiometry, whereas a square planar geometry was proposed for the nickel and copper complexes, slightly distorted in the case of the latter.The antiulcer activity of 5-chlorosalicylaldehyde derivative and its nickel and copper complexes were evaluated in ethanol-induced gastric mucosal injury in rats. This Schiff base and its complexes promote ulcer protection as ascertained by the comparative decrease in ulcer areas, and inhibition of edema and leucocyte infiltration of the submucosal layer.     

Mixed Ligand Complexes of 5-arylazo-8-hydroxyquinoline and α-amino Acids with Co(II), Ni(II) and Cu(II)

Ten mixed ligand complexes of the type [M(X-QA)(aa)] and [Ni(X-QA)₂(Haa)(H₂O)],where X-HQA=5-arylazo-8-hydroxyquinoline derivatives, M=Co(II) orCu(II) and Haa=glycine (gly), alanine (ala) or methionine (met), have been prepared. The complexes have been characterized by elemental analysis, IR and electron spectra and thermal analysis. A tetrahedral structure has been proposed for the cobalt(II) and copper(II) complexes with bidentate coordination of amino acids. The nickel(II) complexes have been assigned an octahedral structure with the amino acids acting as monodentate ligands. The thermal behaviour of the complexes has been studied before and after γ-irradiation. This revised version was published online in August 2006 with corrections to the Cover Date.     

Synthesis and Characterization of Some Mixed Ligand-Selenito and Tellurito Chromium(III) Complexes

New mixed ligand Cr(III) complexes were prepared where diamine or oxalato ligands are coordinated together with either tellurito, selenito, or hydrogenselenito ions to form nine octahedral complexes. The complexes were characterized by chemical analyses, IR and UV-visible spectra, magnetic, and conductivity measurements. The tellurito and selenito ligands act as monodentate ligands, coupled with the bidentate diamine ligands. On the other hand, they act as bidentate chelate ligands when coordinated together with the oxalate ligand. However, hydrogenselenite ion act as a monodentate ligand coupled with the oxalate ligand. IR spectra indicated that the inorganic ligands are coordinated to the Cr(III) ion through their oxygen atoms. One of the bulky diamine molecules, 1,2-pn or 1,3-pn, was freed from the coordination sphere of Cr(III) on the addition of the bulky inorganic anions and was replaced by two water molecules.     

Synthesis and characterization of Ni(II) and Co(II) complexes of Schiff bases derived from 3,4-dimethyl-Δ3-tetrahydrobenzaldehyde and 4,6-dimethyl-Δ3-tetrahydrobenzaldehyde and glycene

The Schiff bases derived from 3,4-dimethyl-Δ³-tetrahydrobenzaldehyde or 4,6-dimethyl-Δ³-tetrahydrobenzaldehyde and glycine and their complexes with nickel (II) and copper (II) were synthesized and investigated. All compounds were characterized by elemental analyses, conductivity measurements, and FT-IR spectroscopy. The Schiff base ligands and their complexes were further characterized by ¹H NMR. The results suggest that the Schiff base acts as a bidentate ligand, which bonds to the metal ions through the imino nitrogen and carboxylate oxygen. The potassium salts of the Schiff bases are 1 : 1 electrolytes but all the complexes are nonelectrolytes. The article was submitted by the authors in English.     

Mixed ligand complexes of Cu(II)-2-(2-pyridyl)-benzimidazole and aliphatic or aromatic dicarboxylic acids: Synthesis, characterization and biological activity

The synthesis and structural characterization of mixed ligand complexes derived from 2-(2-pyridyl)-benzimidazole (PBI) (1ry ligand) and aliphatic or aromatic dicarboxylic acids (2ry ligand) are reported. Cu(II) complexes were characterized on the bases of their elemental analyses, IR, ESR and thermal analyses. The elemental analysis indicated the formation of mixed ligand complexes in a mole ratio 1:1:1 (Cu:L(1):L(2)), L(1)=PBI and L(2)=oxalic acid, phthalic acid or malonic acid. IR spectra showed that PBI acts as a neutral bidentate coordinated to the Cu(II) via the pyridyl and imidazolyl nitrogen atoms. The dicarboxylic acids are bidentate with monodentate carboxylate groups. Thermal decomposition study of complexes was monitored by thermogravimetric (TG) and derivative thermogravimetric (DTG) analysis in N(2) atmosphere. The decomposition course and steps were analysed and the activation parameters of the nonisothermal decomposition were calculated from the TG curves and discussed. The isolated metal chelates were screened for their antimicrobial activities and the results are reported, discussed and compared with some known antibiotics.     

Thermodynamics of metalligand bond formation : XXX. Base adducts of mercury(II) cyanide

Thermodynamic data, obtained by calorimetric titration in acetonitrile solution, are reported for the reaction of mercury(II) cyanide with sixteen nitrogenous bases. As a Lewis acid Hg(CN)₂ is comparable to Hg(CCl₃)₂ and forms moderately stable, 3-coordinate adducts with unidentate N-bases in solution. Much more stable adducts are formed with bidentate bases and there is much less steric resistance to the formation of chelate, 4-coordinate adducts than is shown by Hg(CCl₃)₂.     

Infrared and raman spectra,and stereochemistries of 1:2 trimethylphosphine complexes of group V trihalides,MX3 · 2P(CH3)3 and MX3 · 2P(CD3)3 (where M = P or As and X = Cl or Br); spectra of 1,2-bisdimethylphosphinoethane and chelate complexes with group v trihalides

The 1 : 2 trimethylphosphine (deuterated and non-deuterated) adducts of the Group V trihalides MX₃ (where M = P or As and X = Cl or Br) are prepared and examined by vibrational spectroscopy. The forced cis-configuration complexes MX₃ · bdpe where bdpe is the bidentate ligand 1,2-bisdimethylphosphinoethane are also prepared and examined spectroscopically. Comparison of the Raman and IR spectra of these complexes shows the monodentate adducts to be covalent monomers having a trans-stereochemistry in the solid state. Normal coordinate calculations in C_2v symmetry (trans-stereochemistry) are performed for all monodentate adducts reported.     

Phosphaalkenyl germylenes and their gold, tungsten and molybdenum complexes

The new bis(phosphaalkenyl) germanium(II) compound (NHC)Ge(CCl=PMes*)(2) reacts with L(2)M(CO)(4) (M = Mo, W) to give bidentate complexes with an unexpected coordinating behaviour involving the Ge(II) centre and one phosphorus atom, and with AuI or Me(2)SAuCl to afford the monodentate complexes coordinated at the germanium(II) atom.     

TRANSITION METAL COMPLEXES OF AMINOPHOSPHONIC ACID ANALOGUES OF METHIONINE AND ALANINE IN AQUEOUS SOLUTION

Abstract

The stoichiometrics and stability constants of the nickel(II), copper(II) and zinc(II) complexes of l-amino-3-methylthiopropanephosphonic acid (MetP) and 1-amino-ethanephosphonic acid (a-AlaP) have been determined pH-metrically at 25°C at an ionic strength of 0.2 mol dm^?3 (KC1). From the stability data and the absorption spectra of the complexes it has been established that simple aminophosphonic acids coordinate to the nickel(II) and copper(II) ions forming chelate complexes in which the metal binding mode is bidentate with the {NH₂, PO₃ ^2-} donor set. ³¹P and ¹H NMR measurements showed that MetP and α-AlaP exhibit similar properties in the presence of zinc(II) ions, but the ligand reacts to form a cyclic phosphonoamidate in neutral and slightly alkaline solution in the Zn(II)-α-AlaP system and at slightly acidic conditions in the Zn(II)-MetP system. This difference reveals that the latter ligand at pH > 7 prefers Zn(II) coordination involving all possible (amino, phosphonate and thioether sulfur) donor groups.     

Coordination behavior and biopotency of N and S/O donor ligands with their palladium(II) and platinum(II) complexes

Some metal complexes of Schiff bases have been prepared by the interactions of palladium(II) and platinum(II) chloride with 5-chloro-1,3-dihydro-3-[2-(phenyl)-ethylidene]-2H-indol-2-one-hydrazinecarbothioamide(L¹H) and 5-chloro-1,3-dihydro-3-[2-(phenyl)-ethylidene]-2H-indol-2-one-hydrazinecarboxamide(L²H), in bimolar ratios. All the new compounds have been characterized by elemental analyses, conductance measurements, molecular weight determinations, IR and ¹H NMR spectral studies. The spectral data are consistent with a square planar geometry around Pd(II) and Pt(II) in which the ligands act as neutral bidentate and monobasic bidentate ligands, coordinating through the nitrogen and sulfur/oxygen atoms. Free ligands and their metal complexes were screened for their antimicrobial activity on different species of pathogenic fungi and bacteria and their biopotency has been discussed.     

Photochromism of metal complexes composed of diarylethene ligands and Zn(II), Mn(II), and Cu(II) hexafluoroacetylacetonates

Metal complexes composed of bidentate 1,2-bis(2-methyl-5-(4-pyridyl)-3-thienyl)perfluorocyclopentene (1a) and monodentate 1-(2-methyl-5-phenyl-3-thienyl)-2-(2-methyl-5-(4-pyridyl)-3-thienyl)perfluorocyclopentene (2a) photochromic ligands and M(hfac)(2) (M = Zn(II), Mn(II), and Cu(II)) were prepared, and their photoinduced coordination structural changes were studied. X-ray crystallographic analyses showed the formation of coordination polymers and discrete 1:2 complexes for bidentate and monodentate ligands, respectively. The complexes underwent reversible photochromic reactions by alternate irradiation with UV and visible lights in solution as well as in the single-crystalline phase. Upon photoirradiation with UV and visible light, the ESR spectra of the copper complexes of 1a reversibly changed. While the open-ring isomer gave an axial-type spectrum, the photogenerated closed-ring isomer showed a rhombic-type spectrum. This indicates that the photoisomerization induced the change in the coordination structure.     

Synthesis, thermal and infrared spectroscopic studies of hydrazinated mixed metal fumarates

A series of hydrazinated complexes of mixed nickel manganese zinc ferrous fumarates were synthesized from aqueous metal chlorides solution and sodium fumarate–hydrazine hydrate mixture. These complexes were characterized by chemical analysis, infrared spectroscopy, thermogravimetry-differential scanning calorimetry and isothermal mass loss studies. The hydrazine ligand in these complexes shows bidentate bridging nature while, carboxylate ion displays monodentate behaviour. Thermal decomposition studies indicate 3-step decomposition, involving 2-step dehydrazination and 1-step decarboxylation. The thermal decomposition residues were characterized by X-ray diffractometry, transmission electron microscopy and infrared spectroscopy.