Adel Z. El-Sonbati

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.

Supramolecular structure, mixed ligands and substituents effect on the spectral studies of oxovanadium(IV) complexes of bioinorganic and medicinal relevance.

An interesting series of heterocyclic mixed ligand of oxovanadium(IV) complexes have been synthesized by the reaction of vanadium(IV) sulfate with rhodanine azo (HL(n)) in the presence of β-diketon (LH). The elemental analysis, magnetic moments, spectral (UV-Vis, IR, (1)HNMR and ESR) with thermal studies were used to characterize the isolated complexes. The IR showed that the ligands (HL(n) and LH) act as a monobasic bidentate through the (NN), oxygen keto moiety and oxygen atom of the two enolate groups thereby forming a six-membered. The molar conductivities show that all the complexes are non-electrolytes. The ESR spectra indicate that the free electron is in d(xy) orbital. The calculated bonding parameter indicates that in-plane σ-bonding is more covalent than in-plane π-bonding. The coordination geometry around oxovanadium(IV) in all complexes is a hex-coordinated trans octahedral, with one bidentate ligand (L(n)), and one bidentate ligand (L). Electronic and magnetic data proposed the octahedral structure for all complexes under investigation. ESR spectra of VO(2+) reveal data that confirmed the proposed structure. The value of covalency factor (β(1)(∗))(2) and orbital reduction factor K accounts for the covalent nature of the complexes. All electronic transitions were assigned. The Hammetts constant is also discussed.

Polymer complexes XXXVII novel models and structural of symmetrical poly-Schiff base on heterobinuclear complexes of dioxouranium(VI)

Some binary and ternary novel complexes of dioxouranium(VI) with 5-vinylsalicylaldehyde (VSH) have been prepared and characterized by various physico-chemical techniques. The amine exchange reactions of coordinated poly-Schiff bases in these complexes have been also carried out which give symmetrical tetradentate poly-Schiff base complexes. Metal exchange reaction of these dioxouranium(VI) complexes with copper(II) gives the corresponding Cu(II) complexes. Reaction of tetradentate poly-Schiff base complexes of Cu(II) so obtained with ZrCl4 gives heterobinuclear polymer complexes. Magnetic, electronic and IR spectral information commensurate that configurations of square planar copper(II) polymer complexes. All the polymer complexes are coloured and appear to be nonelectrolytes in DMF. The ligands behave as bi-(O, O) and tetradentate (N2, O2) donors. El-Sonbati equation was used to evaluate the symmetric stretching frequency from which the fU-O and fUO, UO- were calculated.

Structural and models of dioxouranium(VI) with rhodanine azodyes--V.

The synthesis of several new coordination compounds of dioxouranium(VI) heterochelates with bidentate rhodanineazol compounds derived from rhodanine are described. The ligands and uranyl complexes have been charcaterized by various physico-chemical techniques. The bond lengths and the force constants have been calculated from asymmetric stretching frequency of O-U-O group. The infrared spectral studies showed a monobasic bidentate behaviour with the oxygen and azonitrogen donor system. The ligands contain intramolecular hydrogen bonds.

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.

Stereochemistry of Uranyl Complexes of New Heterocyclic Nitrogen Containing Aldehydes. I. Novel Relationship for O-U-O Frequencies Center

Abstract New series of uranyl complexes derived from 7-formyl-8-hydroxy quinoline with hydrazine hydrate (HL1), methyl hydrazine (HL2), 1,2-diaminoethane (HL3), 1,2-diaminobenzene (HL4) and 2-aminopyridine (HL5) have been prepared and characterized by elemental analyses, (1H NMR and 13C NMR, electronic and vibrational spectra) and different physical techniques. The magnetic and spectral data suggest a distorted octahedral structure for all complexes. The labile EtOH molecule in compounds (5), (7) and (9) is equatorially bonded to the uranium ion and its hydrogen is bonded to the axial oxygen of the uranyl moiety. The ligands contain intramolecular hydrogen bonds. The FU-O(mydn/Ao) and the bond length RU-O(Ao) of the bond were calculated from the IR data. In the present work it has been proposed a novel relationship between symmetric “V1” and asymmetric “v3” O-U-O frequencies independent on the masses of oxygen (Mo) and uranium (Mu) atoms.

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: XLIX—Supramolecular modeling of bonding in novel rare earth polymeric rhodanine drug complexes

Novel supramolecular rare earth polymeric hydrazone complexes of 5-sulphadiazineazo-3-phenyl-2-thiaxo-4-thiazolidinone (HL) of the composition [(Ln)(2)(HL)(3)(NO(3))(6)](n) (where Ln = La(1), Y(2), Pr(3), Nd(4), Sm(5), Gd(6) and Ho(7)) have been prepared and characterized on the basis of their chemical analyses, magnetic measurements, conductance, visible and IR spectral data. Composition, conductance and IR spectral data of complexes show that all these act as a tetradentate ligand. Electronic spectra indicate weak covalent character in the metal-ligand bond. The spectra of Nd(3+) and Ho(3+) show characteristic f-f transitions and the metal-ligand covalency in % has been evaluated. The spectral properties of the above polymeric complexes are also discussed.

Stereochemistry of new nitrogen containing heterocyclic aldehyde. IX. Spectroscopic studies on novel mixed-ligand complexes of Rh(III).

Mono, bis and tris complexes of rhodium(III) oxine (systematic name 8-hydroxy-7-quinolinecarboxaldehyde) and mixed ligand have been prepared. The amine exchange reaction of coordinated Schiff base in these complexes has also been carried out, which gives symmetrical tetradentate Schiff base complexes. The complexes are characterized by elemental and thermal analysis, IR, magnetic and electronic spectral analysis methods were also employed as well as conductivity measurements. An octahedral structure is proposed for all the new complexes in which chloride is attached to the metal ion in 1:1; 1:2 (metal:ligand) ratio. The spectral data were utilized to compute the important ligand field parameter B, beta and Dq. The B-values suggest a strong covalency in the metal-ligand sigma-bond and the Dq-values indicate a medium strong ligand field. 1H NMR spectra show that the tris (ligand) complex is cis isomer. IR spectra show that the ligand is mono-basic bidentate.