M.A. Diab

Structural and characterization of novel copper(II) azodye complexes.

The synthetic methods of novel Cu(II) and adduct complexes, with selective azodyes containing nitrogen and oxygen donor ligands have been developed, characterized and presented. The prepared complexes fall into the stoichiometric formulae of [Cu(L(n))(2)](A) and [Cu(L(n))(2)(Py)(2)](B), where two types of complexes were expected and described. In type [(A) (1:2)] the chelate rings are six-membered/four coordinate, whereas in type [(B) (1:2:2)] they are six-membered/six coordinate. The important bands in the IR spectra and main (1)H NMR signals are tentatively assigned and discussed in relation to the predicted assembly of the molecular structure. The IR data of the azodye ligands suggested the existing of a bidentate binding involving azodye nitrogen and C-O oxygen atom of enolic group. They also showed the presence of Py coordinating with the metal ion. The coordination geometries and electronic structures are determined from the framework of the proposed modeling of the formed novel complexes. The complexes (1-5) exist in trans-isomeric [N,O] solid form, while adduct complexes (6-10) exist in trans isomeric (Py) form. The square planar/octahedral coordination geometry of Cu(II)/adduct is made up of an N-atom of azodye, the deprotonated enolic O-atom and two Py. The azo group was involved in chelation for all the prepared complexes. ESR spectra show the simultaneous presence of a planar trans and a nearly planar cis isomers in the 1:2 ratio for all N,O complexes [Cu(L(n))(2)]. The ligands in the dimmer are stacked over one another. In the solid state of azo-rhodanine, the dimmers have inter- and intramolecular hydrogen bonds. Interactions between the ligands and Cu(II) are also discussed.

Polymer complexes: XLXII-interplay of coordination π-π stacking and hydrogen bonding in supramolecular assembly of [sulpha drug derivatives-N,S:N,O] complexes.

A novel series of nickel(II) polymer complexes of 5-sulphadiazineazo-3-phenylamino-2-thio-4-thiazolidinone (HL₁), 5-sulphamethazine-3-phenylamino-2-thioxo-4-thiazolidinone (HL₂), 5-sulphamethoxazole-3-phenylamino-2-thioxo-4-thiazolidinone (HL₃), 5-sulphacetamide-3-phenyl-2-thioxo-4-thiazolidinone (HL₄) and 5-sulphaguanidine-3-phenylamino-2-thioxo-4-thiazolidinone (HL₅) were prepared and characterized. IR spectra show that HL(n) (n=1-5) is coordinated to the metal ion in a neutral tetradentate manner with NSNO donor sites of NH (hydrazones), NH (3-phenylamine), carbonyl group and Ph-NH. The title [Ni₃(HL(n))₂(μ-OAc)₂(OAc)₄](n) consists of three Ni(II) atoms linked by interchain π-π interaction are observed between aromatic rings of two ligands (HL(n)) which are further doubly bridged two adjacent nickel atoms by acetate group. The geometrical structures of these complexes are found to be octahedral. The nature of bonding and the stereochemistry of the complexes have been deduced from elemental analyses, thermal, infrared, ¹H NMR, electronic spectra, magnetic susceptibility and conductivity measurements. The richness of electronic spectral in these complexes is also supporting evidence for the trinuclearity of the Ni(II) polymer complexes.

Polymer complexes. LIII. Supramolecular coordination modes and structural of novel sulphadrug complexes

Novel polymer complexes of copper(II), palladium(II), platinum(II) and cadmium(II) containing homopolymer [4-acrylamido benzene sulphonyl guanidine; (HL)] and various anions (SO₄²⁻, CH₃COO⁻, NO₃⁻, Br⁻ or Cl⁻) have been designed and carried out. Their structures were investigated by elemental analyses, spectral (IR, UV-vis, ¹H NMR and ESR) and magnetic moments. The modes of interactions between the ligand and the metals were discussed, where oxygen (of O=S=O group) and nitrogen atom [of imino nitrogen (NH/N) of the guanidine group] are involved in chelation. The homopolymer shows two types of coordination behaviour. In mononuclear polymer complexes 4 and 6-10, it acts as a neutral bidentate ligand chelated through the NH and O atoms, whereas in the polymer complexes 1-3, 5 and 11, monobasic bidentate ligand is coordinated through the -N and -O atoms. The poly-chelates are of 1:1/1:2 (metal-homopolymer) stoichiometry and exhibit four coordination. On the basis of electronic spectral data and magnetic susceptibility measurement square planar geometry has been proposed. The ESR spectral data provided information about their structure on the basis Hamiltonian parameters and degree of covalency. From the electron paramagnetic resonance and spectral data, the orbital reduction factors were calculated.

Polymer complexes. LVIII. Structures of supramolecular assemblies of vanadium with chelating groups

Oxovanadium(IV) polymer complexes of formulation {[(VO)L](2)}(n) (1) and [(VO)LB](n) (2-4), where H(2)L is tridentate and dianionic ligand (allylazorhodanine) and B is planar heterocyclic and aliphatic base have been prepared and characterized by elemental analyses, IR, (1)H NMR, electronic spin resonance spectra, magnetic susceptibility measurements, molar conductance and thermal studies. The molecular structure shows the presence of a vanadyl group in six-coordinate VNO(3)/VN(3)O(3) coordination geometry. The N,N-donor heterocyclic and aliphatic bas displays a chelating mode of binding with an N-donor site trans to the vanadyl oxo-group. In all polymeric complexes (1-4) the ligand coordinates through oxygen of phenolic/enolic and azodye nitrogen. The molar conductivity data show them to be non-electrolytes. All the polymer complexes are ESR active due to the presence of an unpaired electron. The calculated bonding parameters indicate that in-plane σ bonding is more covalent than in-plane π bonding. From the electronic, magnetic and ESR spectral data suggest that all the oxovanadium(IV) polymer complexes have distorted octahedral geometry. The thermal decomposition process of the polymeric complexes involves three decomposition steps.

Polymer complexes. Part IV—Thermal stability of poly(8-quinolyl acrylate) and the polymers of the complexes of 8-quinolyl acrylate with some transition metal salts

Abstract Poly(8-quinolyl acrylate) and the polymers of the complexes of 8-quinolyl acrylate with some transition metal bromides and uranyl acetate have been prepared and characterized by elemental analyses, electronic and vibration spectroscopic studies and magnetic moments. The thermal stabilities of the homopolymer and the polymer complexes were studied by means of thermogravimetric analysis. The activation energies of the degradation of the homopolymer and polymer complexes were calculated.

Polymer complexes: Part VIII—Thermal stability of poly(2-acrylamidopyridine) and polymer complexes of 2-acrylamidopyridine with some transition metal chlorides

Abstract Poly(2-acrylamidopyridine) homopolymer and polymer complexes of 2-acrylamidopyridine with some transition metal chlorides have been prepared and characterized by elemental analyses, electronic and vibration spectroscopic studies and magnetic moments. The thermal stabilities of the homopolymer and the polymer complexes were studied by means of thermogravimetric analysis. The activation energies of the degradation of the homopolymer and polymer complexes were calculated.

Polymer complexes: 25. Complexing ability of poly(5-vinylsalicylidene-2-aminopyridine) towards different metal(ii) salts

Mononuclear and binuclear complexes of poly(5-vinylsalicylidene-2-aminopyridine)† were prepared by the reaction of the homopolymer with copper(ii), cobalt(ii), nickel(ii), cadmium(ii), dioxouranium(vi) and palladium(ii) salts. Metal(ii) acetates and palladium chloride were found to give mononuclear complexes, while cupric chloride gave a binuclear complex. The polymer complexes have been characterized on the basis of elemental analysis, u.v. and i.r. spectroscopy, and magnetic susceptibility measurements. The stereochemistry and the nature of the complexes are markedly dependent upon the molar ratios of the reactants, the pH of the system and the nature of the anions involved. In all of the complexes the homopolymer was chelated to the metal ion through the nitrogen atom of the azomethine group and the oxygen atom of the phenolic group. The low value of the magnetic moment of the binuclear copper complex is due to an antiferromagnetic interaction between two adjacent copper atoms. The ligand field parameters have been calculated and related to the electronic environments. The electronic absorption of the homopolymer was investigated in organic solvents of varying polarities and buffer solutions of different pH, and the behaviour in the latter has been utilized in calculating the pKa of the phenol group.

Polymer complexes: Part VI—Thermal stability of poly(2-acrylamidophenol) homopolymer and complexes of poly(2-acrylamidophenol) with some transition metal salts

Abstract Poly(2-acrylamidophenol) homopolymer and complexes of poly(2-acrylamidophenol) with Cu II, Ni II, Co II, Cd II chlorides and uranyl acetate were prepared and characterized by elemental analyses, IR, UV and magnetic measurements. Thermal stabilities of the polymer complexes were studied using thermogravimetric analysis. The activation energies of the degradation of the polymer complexes were calculated.

Thermal stability and degradation of chitosan modified by benzophenone

N-(biphenylmethylidenyl) chitosan polymer was prepared, characterized and thermal stability was compared with chitosan. Thermal degradation products of the modified polymer were identified by GC-MS technique. It seems that the mechanism of degradation of the prepared polymer is characterized by formation of low molecular weight radicals, followed by random scission mechanism along the backbond chain.

Polymer complexes. XXXX. Supramolecular assembly on coordination models of mixed-valence-ligand poly[1-acrylamido-2-(2-pyridyl)ethane] complexes.

The build-up of polymer metallic supramolecules based on homopolymer (1-acrylamido-2-(2-pyridyl)ethane (AEPH)) and ruthenium, rhodium, palladium as well as platinum complexes has been pursued with great interest. The homopolymer shows three types of coordination behaviour. In the mixed valence paramagnetic trinuclear polymer complexes [(11)+(12)] in the paper and in mononuclear polymer complexes (1)-(5) it acts as a neutral bidentate ligand coordinating through the N-pyridine and NH-imino atoms, while in the mixed ligand diamagnetic poly-chelates, which are obtained from the reaction of AEPH with PdX2 and KPtCl4 in the presence of N-heterocyclic base consisting of polymer complexes (9)+(10), and in monouclear compounds (6)-(8), it behaves as a monobasic bidentate ligand coordinating through the same donor atoms. In mononuclear compounds (13)+(14) it acts as a monobasic and neutral bidentate ligand coordinating only through the same donor atoms. Monomeric distorted octahedral or trimeric chlorine-bridged, approximately octahedral structures are proposed for these polymer complexes. The poly-chelates are of 1:1, 1:2 and 3:2 (metal-homopolymer) stoichiometry and exhibit six coordination. The values of ligand field parameters were calculated. The homopolymer and their polymer complexes have been characterized physicochemically.