Synthesis and spectral studies of new N2S2 and N2O2 Mannich base ligands and their metal complexes

New Mannich bases bis(thiosemicarbazide methyl) phosphinic acid H₃L¹ and bis(1-phenylsemicarbazide methyl) phosphinic acid H₃L² were synthesized from condensation of phosphinic acid and formaldehyde with thiosemicarbazide and 1-phenylsemicarbazide, respectively. Monomeric complexes of these ligands, of general formula K₂[Cr^III(L ⁿ )Cl₂], K₃[Fe^II(L¹)Cl₂], K₃[Mn^II(L²)Cl₂], and K[M(L ⁿ )] (M = Co(II), Ni(II), Cu(II), Zn(II) or Cd(II); n = 1, 2) are reported. The mode of bonding and overall geometry of the complexes were determined through IR, UV-Vis, NMR, and mass spectral studies, magnetic moment measurements, elemental analysis, metal content, and conductance. These studies revealed octahedral geometries for the Cr(III), Mn(II), and Fe(II) complexes, square planar for Co(II), Ni(II), and Cu(II) complexes and tetrahedral for the Zn(II) and Cd(II) complexes. Complex formation via molar ratio in DMF solution has been investigated and results were consistent to those found in the solid complexes with a ratio of (M : L) as (1 : 1).     

Coenzyme M studies with nickel(II) compounds: Synthesis,structure, spectra and redox behaviors

Nickel(II) complexes of 1,6-bis(pyridyl)-2,5-dithiahexane (L¹), 1,7-bis(2′-pyridyl)-2,6-dithiaheptane (L²) and 1,9-bis(2′-pyridyl)-2,5,8-trithianonane (L³) have been prepared and their spectroscopic and redox behaviors were studied. [Ni(II)L¹(H₂O)₂](ClO₄)₂, and [Ni(II)L³(H₂O)](ClO₄)₂ were crystallized in single crystal form; their structures were solved by X-ray crystallography. The structures of the complexes are of distorted octahedral geometry. A red shift in the electronic spectra and a positive potential shift in electrochemical studies were detected during the addition of the sodium salt of 2-mercaptoethanesulfonic acid (CoM) to Ni(II) complexes containing L¹ and L². The high redox potential shifting difference (PSD) was observed with the addition of CoM to [NiL¹]²⁺, which accounts for the axial coordination of CoM with the nickel ion. However, [Ni(II)L³]²⁺ does not respond well with CoM addition due to the structural limitation around the Ni(II) ion. A destabilization of [Ni(II)L¹]²⁺ and [Ni(II)L²]²⁺ complexes and stabilization for [Ni(II)L³]²⁺ were noticed in their redox studies and these trends were inversely changed during anaerobic CoM addition to Ni(II) complexes. A nephelauxetic effect (β values) has been shown to establish a good relation with PSD.     

Synthesis and spectral studies of macrocyclic Pb(II), Zn(II), Cd(II) and La(III) complexes by template reaction of 1,2-bis(2-formylphenyl)ethane with metal nitrate and various diamine

Eight new macrocyclic complexes were synthesized by template reaction of 1,4-bis(3-aminopropoxy)butane or (±)-trans-1,2-diaminocyclohexane with metal nitrate and 1,2-bis(2-formylphenyl)ethane and their structures were proposed on the basis of elemental analysis, FT-IR, UV-Vis, molar conductivity measurements, ¹H NMR and mass spectra. The metals to ligand molar ratios of the complexes were found to be 1: 1. The complexes are 1: 2 electrolytes for Cd(II), Pb(II) and Zn(II) complexes and 1: 3 electrolytes for La(III) as shown by their molar conductivities (Λ_m) in DMSO at 10⁻³ mol L⁻¹. Due to the existence of free ions in these complexes, such complexes are electrically conductive. The configurations of Cd(II) and Zn(II) complexes were proposed to probably tetrahedral, La(III) complexes are octahedral and Pb(II) complexes are octahedral geometry in the L¹ complex and tetrahedral geometry in the L² complex.     

Synthesis and structural studies of new Mannich base ligands and their metal complexes

The new Mannich bases bis(1,4-diphenylthiosemicarbazide methyl) phosphinic acid H₃L¹ and bis(1,4-diphenylsemicarbazide methyl) phosphinic acid H₃L² were synthesised from the condensation of phosphinic acid, formaldehyde with 1,4-diphenyl thiosemicarbazide and 1,4-diphenylsemicarbazide, respectively. Monomeric complexes of these ligands, of general formulae K₂[Cr^III(L ⁿ )Cl₂], K₃[Mn^II(L ⁿ )Cl₂] and K[M(L ⁿ )] (M = Co(II), Ni(II), Cu(II), Zn(II) or Hg(II); n = 1, 2), are reported. The mode of bonding and overall geometry of the complexes were determined through physico-chemical and spectroscopic methods. These studies revealed octahedral geometries for the Cr(III), Mn(II) complexes, square planar for Co(II), Ni(II) and Cu(II) complexes and tetrahedral for the Zn(II) and Hg(II) complexes.     

Etude des complexes sulfosalicylate de cuivre(III), nickel(II), cobalt(II) et uranyle(II) a l'aide d'une resine echangeuse de cations: Study of the sulphosalicylate complexes ofcopper(II), nickel(II), cobalt(II) and uranyl(II) by means of cation-exchange resins.

Study of the sulphosalicylate complexes of copper(II), nickel(II), cobalt(II) and uranyl(II) by means of cation-exchange resins.The conditional stability constants of the 1:1 complexes of the sulphosalicylate ions (L^3-) with copper(II), nickel(II), cobalt(II) and uranyl ions have been determined in a sodium perchlorate solution (0.1 M) and at various pH values by a cation-exchange method based on Schubert's procedure. The limits of application of the method are discussed. The variation with pH of the conditional stability constants can be explained by the existence of the complexes: CuH₂L, CuHL, CuL^-; NiH₂L⁺, NiHL, NiL^-; CoHL, CoL^-; UO₂H₂L⁺, UO₂HL, UO₂L^-, UO₂LOH^2-. The stability constants of these complexes are reported. Distribution diagrams of the various complexes of each element with pH and total concentration of sulphosalicylate parameters are given.     

Heteronuclear complexes of oxorhenium(V) with Fe(III), Co(II), Ni(II), Cu(II), Cd(II) and UO2(VI) and their biological activities

Heteronuclear complexes containing oxorhenium(V), with Fe(III), Co(II), Ni(II), Cu(II), Cd(II) and UO₂(VI) ions were prepared by the reaction of the complex ligands [ReO(HL¹)(PPh₃)(OH₂)Cl]Cl (a) and/or [ReO(H₂L²)(PPh₃)(OH₂)Cl]Cl (b), where H₂L¹?=?1-(2-hydroxyphenyl)butane-1,3-dione-3-(5,6-diphenyl-1,2,4-triazine-3-ylhydrazone) and H₃L²?=?1-(2-hydroxyphenyl)butane-1,3-dione-3-(1H-benzimidazol-2-ylhydrazone), with transition and actinide salts. Heterodinuclear complexes of ReO(V) with Fe(III), Co(II), Ni(II), Cu(II) and Cd(II) were obtained using a 1?:?1 mole ratio of the complex ligand and the metal salt. Heterotrinuclear complexes were obtained containing ReO(V) with UO₂(VI) and Cu(II) using 2?:?1 mole ratios of the complex ligand and the metal salts. The complex ligands a and b coordinate with the heterometal ion via a nitrogen of the heterocyclic ring and the nitrogen atom of the C=N⁷ group. All transition metal cations in the heteronuclear complexes have octahedral configurations, while UO₂(VI)?complexes have distorted dodecahedral geometry. The structures of the complexes were elucidated by IR, ESR, electronic and ¹H NMR spectra, magnetic moments, conductance and TG-DSC measurements. The antifungal activities of the complex ligands and their heteronuclear complexes towards Alternaria alternata and Aspergillus niger showed comparable behavior with some well-known antibiotics.     

Composition and stability of copper(II), nickel(II), and cobalt(II) complexes with mono- and bis(2-carboxy)-2-pycolylamine

Complexation of N-(2-pyridyl)methyl-3-aminopropionic (HL¹) and N-(2-pyridyl)methyliminodipropionic (H₂L²) acids with copper(II), nickel(II), and cobalt(II) ions is studied. The composition of complexes is determined using the Starik–Barbanel relative yield method. The acid dissociation constants of HL¹ and H₂L² are determined potentiometrically; the stability constants of HL¹ and H₂L² complexes with metal ions are calculated.     

The coordination chemistry of simple phospholes: Complexes of nickel(II), palladium(II) and platinum(II)

The reactions between four very simply substituted phospholes and the chlorides of Ni(II), Pd(II) and Pt(II) are described. The phospholes 1-phenylphosphole, 3-methyl-1-phenyl-phosphole and 3,4dimethyl-1-phenylphosphole all readily form bis-complexes of formula L₂MCl₂ [L = phosphole ligand and M = Ni(II), Pd(II) or Pt(II)] or tris-complexes of formula L₃MCI₂. 1-n-Butyl-3,4-dimethylphosphole appears to form stable complexes only with Ni(II). Evidence is put forward which indicates that the L₂MCl₂ complexes exist in a four-coordinate, square-planar monomeric/five coordinate equilibrium while the L₃MCl₂ complexes are primarily the ionic species [L₃MCl]⁺ Cl^? in solution. Comparisons are made with the behaviour of other simple phospholes which do not form Ni(II) complexes and the results are discussed briefly in terms of both aromatic and non-aromatic phosphole models.     

Dioxygen activation with a cytochrome P450 model. Characterization and electrochemical study of new unsymmetrical tetradentate Schiff-base complexes with iron(III) and cobalt(II)

Salicylaldehyde or 5-bromosalicylaldehyde react with 2,3-diaminophenol to give two unsymmetrical Schiff-bases H₂L¹, H₂L², respectively. With Fe(III) and Co(II), these ligands lead to four complexes: Fe(III)ClL¹, Fe(III)ClL², Co(II)L¹, Co(II)L². The structures of these complexes were determined by mass spectroscopy, infrared and electronic spectra. Cyclic voltammetry in dimethylformamide (DMF) showed irreversible waves for both ligands. In the same experimental conditions, Fe(III)ClL¹ exhibited a reversible redox couple Fe(III)/Fe(II) while the three other complexes showed quasi-reversible systems. The behavior of some of these complexes in the presence of dioxygen and the comparison with cytochrome P450 are described.     

Synthesis and characterization of substituted aminobiphenylglyoximes and their complexes with some transition metals

In this study, four different new vic-dioximates, [L¹H₂] N-(4-ethylphenyl)amino-biphenylglyoxime, [L²H₂] N-(4-butylphenyl)aminobiphenylglyoxime, [L³H₂] N-(4-aminoacetanilide)aminobiphenylglyoxime, and [L⁴H₂] N-(thiazol-2-yl-aminobiphenylglyoxime are synthesized from anti-4′-biphenylchloroglyoxime and the corresponding substituted aromatic amines. The Co(II), Ni(II), and Cu(II) complexes of these ligands are prepared. The structures of these new ligands and their complexes are proposed based upon IR, ¹H, and ¹³C NMR spectral data, mass spectroscopy, magnetic susceptibility measurement, and elemental analyses. The text was submitted by the authors in English.     

Studies in stability constants of schiff base hydrazone complexes with transition metal ions. Effect of ligand on seed germination

Spectrophotometric investigation of Cu (II), Ni(II), Co(II), and Fe(III) complexes with 2,4-dihydroxyacetophonone 2,4-dichlorobenzoylhydrazone (H₂L¹) and 2,4-didydroxy-5-nitroacetophenone 2,4-dichlorobenzoylhydrazone (H₂L²) shows 1: 1 and 1: 2 complex formation between the pH range of 3.0 to 6.0 and also studied by jobs variation method at 0.1 M ionic strength at 30 ± 1°C specrtophotometrically. The conditional stability constants are determined for 1: 1 complexes. Effect of H₂L¹ and H₂L² ligand and its complexes on seed germination is studied.     

New homoleptic metal complexes of Schiff bases derived from 2,4-di-p-tolyl-3-azabicyclo[3.3.1]nonan-9-one

New bidentate Schiff-base ligands 2-(2,4-di-p-tolyl-3-azabicyclo[3.3.1]nonan-9-ylidene)hydrazinecarbothioamide HL¹ and 2-(2,4-di-p-tolyl-3-azabicyclo[3.3.1]nonan-9-ylidene)hydrazinecarboxamide HL² were synthesized from the condensation of 2,4-di-p-tolyl-3-azabicyclo[3.3.1]nonan-9-one with thiosemicarbazide and semicarbazide, respectively. Homoleptic complexes of these ligands, of general formula K[Cr(L ⁿ )₂Cl₂], K₂[Mn(L ⁿ )₂Cl₂], K₂[Fe(L¹)₂Cl₂] and [M(L ⁿ )₂] (where M = Co(II), Ni(II) Cu(II), Zn(II), Cd(II), and Hg(II) ions; n = 1 or 2) are reported. The mode of bonding and overall geometry of the complexes were determined through IR, UV-Vis, NMR and mass spectral studies, magnetic moment measurements, elemental analysis, metal content, and conductance. These studies revealed octahedral geometry for Cr(III), Mn(II), and Fe(II) complexes, square planar for Cu(II), Co(II), and Ni(II) complexes and tetrahedral for Zn(II), Cd(II), and Hg(II) complexes.     

Synthesis of copper and zinc chloride complexes with tri- and tetranitrofluorenones. Crystal and molecular structure of 2,4,5,7-tetranitrofluorenone

The complexes MLCl₂ · nH₂O and ML₂Cl₂ · nH₂O, where M = Cu(II), Zn and n = 1–4, were isolated and identified due to the reactions of Cu(II) and Zn(II) chlorides with 2,4,7-trinitrofluorene (L¹), 2,4,7-trinitrofluorenone (L^1a), and 2,4,5,7-tetranitrofluorene (L²). It was shown that, during complex formation, L¹ and L² were oxidized to fluorenones (L^1a, L^2a) and as neutral ligands formed 1: 1 and 2: 1 complexes with metal cations. A single crystal of tetranitrofluorenone (L^2a) was isolated, and its crystal and molecular structure was determined. The complexes were studied by X-ray powder diffraction analysis, their spectral (IR and UV) characteristics were determined, and the structures for the complexes were proposed.     

Synthesis,spectroscopic and electrochemical studies of copper(II) and cobalt(II) complexes of three unsymmetrical vic -dioximes ligands

Cobalt(II) and copper(II) complexes with three dioxime ligands cyclohexylamine-p-tolylglyoxime (L₁H₂), tert-butyl amine-p-tolylglioxime (L₂H₂) and sec-butylamine-p-tolylglyoxime (L₃H₂), have been prepared. The metal to ligand ratios of the complexes were found to be 1?:?2. The Cu(II) complexes of these ligands are proposed to be square planar; the Co(II) complexes are proposed to be octahedral with water molecules as axial ligands. Ligands and complexes are soluble in common solvents such as DMSO, DMF, CHCl₃ and C₂H₅OH. The ligands have been characterized by elemental analysis, IR, UV-VIS, ¹H?NMR, ¹³C?NMR and thermogravimetric analysis (TGA). The complexes were characterized by elemental analysis, IR, UV-VIS, magnetic susceptibility measurements, thermogravimetric analysis (TGA) and electrochemistry. Electrochemical properties of metal complexes show quasi-reversible one-electron redox processes. However, Co(L₁H)₂ and Cu(L₁H)₂ complexes show another oxidation peak in the positive region. This single irreversible oxidation peak is caused by the cyclic ring of the ligand. Data also revealed that the electron transfer rates of metal complexes with L₁H₂ are higher than the other complexes.     

Synthesis and complexation of two new phenylaminoglyoxime ligands

Two new soluble phenylaminoglyoxime ligands, 4-isopropylanilinephenylglyoxime (L¹H₂), 4-benzylpiperidinephenylglyoxime (L²H₂), were prepared by reacting 4-isopropylaniline and 4-benzylpiperidine with chlorophenylglyoxime. Mononuclear nickel(II), cobalt(II), copper(II), zinc(II), and cadmium(II) complexes with these ligands were synthesized. On the basis of the magnetic and spectral evidence a square-planar geometry for Ni(II) and Cu(II) complexes, a tedrahedral geometry for Cd(II) and Zn(II) complexes and octahedral geometry for Co(II) complexes are proposed. These compounds were elucidated by elemental analysis, IR, UV-Vis, and magnetic moments. The ligands were additionally characterized by ¹H NMR and ¹³C NMR spectra.     

Coordination compounds of some d metals with anthrapyridinedione derivatives: Crystal structure of 2-phenyl-4-(piperidyl-1)-anthra[1,2-b]pyridine-7,12-dionium hexabromodicuprate(II) (HL1)2[Cu2Br6]

Complexes of copper(II), nickel(II), and cobalt(II) chlorides and bromides with 2-phenyl-4-(piperidyl-1)-anthra[1,2-b]pyridine-7,12-dione (L¹) and 2-[phenyl-4-(octylamino)-anthra[1,2-b]pyridine-7,12-dione (L²) were synthesized from neutral and acidic media. The molecular and crystal structure of 2-phenyl-4-(piperidyl-1)-anthra[1,2-b]pyridine-7,12-dionium hexabromodicuprate(II) (HL¹)₂[Cu₂Br₆] was determined by X-ray diffraction analysis. The spectral characteristics of L¹ and L² and their complexes are presented. Formation of their complexes in solutions was studied.     

The Cu(II) complexes with bis(pyrazole-1-yl)methane and its derivatives: Synthesis,crystal structure,and magnetic properties

The procedures for the synthesis of the Cu(II) complexes with bis(pyrazole-1-yl)methane (L¹), bis(3,5-dimethyl-4-bromopyrazole-1-yl)methane (L²), and bis(3,5-dimethyl-4-iodopyrazole-1-yl)methane (L³) of the composition Cu₂(L¹)₂Br₄ (I), Cu₂(L²)₂Cl₄ (II), Cu(L³)(NO₃)₂ (III), and Cu(L³)(H₂O)(NO₃)₂ · 2H₂O (IV) were developed. The organic ligands in the above complexes are coordinated to Cu(II) in a bidentate cyclic type through the N(2), N(2′) atoms of the pyrazole rings. The molecular and crystal structures of L², L³, II, III, and IV were determined by X-ray diffraction. The study of the μ_eff(T) function in a temperature interval 2–300 K showed that compound I, which exhibited ferromagnetic exchange interactions in the chains, undergoes transition to antiferromagnetic state with weak ferromagnetism. The exchange antiferromagnetic interactions predominate in compound II.     

Heterodinukleare Cobalt(II)‐, Nickel(II)‐, Kupfer(II)‐, Zink(II)und Palladium(II)‐Komplexe mit einem makrocyclischen Liganden vom Schiff‐Basen‐Typ: Synthesen und Strukturen

Complexes with Macrocyclic Ligands. IV. Heterodinuclear Cobalt(II), Nickel(II), Copper(II), Zinc(II) and Palladium(II) Complexes with a Macrocyclic Ligand of Schiff‐Base Type: Syntheses and Structures The synthesis and properties of nickel(II), copper(II), and palladium(II) complexes, [ML^Ph] ( 3 ; L^Ph = N,N′‐phenylene‐bis(3‐formyl‐5‐tert.‐butyl‐salicylaldimine)), are described. These neutral mononuclear complexes react with metal(II) perchlorate and 1,3‐propylenediamine to form heterodinuclear, macrocyclic, cationic complexes of the type [MM′(L^Ph,3)]²⁺ ( 4 ; M = Ni, Cu, Pd; M′ = Co, Cu, Zn). The structures of the five new compounds [NiCo(L^Ph,3)](ClO₄)₂, [NiCu(L^Ph,3)](ClO₄)₂, [CuCu(L^Ph,3)](ClO₄)₂, [CuZn(L^Ph,3)](ClO₄)₂, and [PdCu(L^Ph,3)](ClO₄)₂ were determined by X‐ray diffraction.     

Preparation and Characterization of Novel Asymmetrical Schiff-Base Ligands Derived from 2-methyl-7-formyl-8-hydroxyquinoline and their Metal Complexes

Two novel asymmetrical Schiff-base ligands, H₂L¹ and H₂L², were prepared by reacting two half-unit Schiff-base compounds with 2-methyl-7-formyl-8-hydroxyquinoline. The two half-unit Schiff-base compounds were initially prepared by condensing dimedone with either ethylenediamine or p-phenylenediamine, respectively. Both ligands are dibasic and contain two sets of NO coordinating sites. Twelve metal complexes were obtained by reacting both ligands with Cu(II), Ni(II), Co(II), Mn(II), Fe(III), VO(IV) cations. The ligands and their metal complexes were characterized by elemental analysis, IR, UV-Vis, ESR and mass spectra, also magnetic moments of the complexes were determined. Visible spectra of the complexes indicated distorted octahedral geometries around the metal cations. ESR spectra indicated mononuclear and dinuclear structures of the complexes of ligands H₂L¹ and H₂L², respectively. Magnetic moments of the complexes were rather low compared with those expected for octahedral geometries and indicated polymeric linkage of the metal complex molecules within their crystal lattices. The insolubility of the metal complexes in most organic solvents support the polymeric structures.     

Synthesis and spectroscopic studies of new binuclear transition metal complexes of Schiff bases derived from 4,6-diacetylresorcinol

Two new series of copper(II), nickel(II), cobalt(II), zinc(II), iron(III), chromium(III), vanadyl(IV) and uranyl(VI) complexes with two bifunctional tridentate Schiff base, H₄L¹ and H₂L² ligands have been prepared. The Schiff base, H₄L¹ and H₂L², ligands were synthesized by the condensation of 4,6-diacetylresorcinol with o-aminophenol or o-phenylenediamine. The ligands are either di- or tetra-basic with two symmetrical sets of either OON or NNO tridentate chelating sites. The ligands and their metal complexes have been characterized by elemental analysis, ¹H-n.m.r., FT-IR, mass, electronic, esr spectra and thermal gravimetric analysis and magnetic susceptibility. With the exception of Co^II ion with H₂L² which afforded a trinuclear complex, a variety of binuclear complexes for the rest of the metal complexes were obtained with the ligands in its di- or tetra-deprotonated forms. The bonding sites are the azomethine and amino nitrogen atoms, and phenolic oxygen atoms. The metal complexes exhibit different geometrical arrangements such as square planar, tetrahedral, square pyramid and octahedral arrangement.