Sanaa M. Emam

Structural studies and anticancer activity of a novel (N6O4) macrocyclic ligand and its Cu(II) complexes

A novel (N6O4) macrocyclic ligand (L) and its Cu(II) complexes have been prepared and characterized by elemental analysis, spectral, thermal (TG/DTG), magnetic, and conductivity measurements. Quantum chemical calculations have also been carried out at B3LYP/6-31+G(d,p) to study the structure of the ligand and one of its complexes. The results show a novel macrocyclic ligand with potential amide oxygen atom, amide and amine nitrogen atoms available for coordination. Distorted square pyramidal ([Cu(L)Cl]Cl·2.5H2O (1), [Cu(L)NO3]NO(3)·3.5H2O (2), and [Cu(L)Br]Br·3H2O (4) and octahedral ([Cu(L)(OAc)2]·5H2O (3)) geometries were proposed. The EPR data of 1, 2, and 4 indicate d1x2(-y)2 ground state of Cu(II) ion with a considerable exchange interaction. The measured cytotoxicity for L and its complexes (1, 2) against three tumor cell lines showed that coordination improves the antitumor activity of the ligand; IC50 for breast cancer cells are ≈8.5, 3, and 4 μg/mL for L and complexes (1) and (2), respectively.

Transition metal complexes of neocryptolepine analogues. Part I: synthesis, spectroscopic characterization, and invitro anticancer activity of copper(II) complexes.

New generation of copper(II) complexes with aminoalkylaminoneocryptolepine as bidentate ligands has been synthesized and it is characterized by elemental analyses, magnetic moment, spectra (IR, UV-Vis, (1)H NMR and ESR) and thermal studies. The IR data suggest the coordination modes for ligands which behave as a bidentate with copper(II) ion. Based on the elemental analysis, magnetic studies, electronic and ESR data, binuclear square planar geometry was proposed for complexes 7a, 7b, square pyramidal for 9a, 9b and octahedral for 8a, 8b, 10a, 10b. The molar conductance in DMF solution indicates that all complexes are electrolyte except 7a and 7b. The ESR spectra of solid copper(II) complexes in powder form showed an axial symmetry with (2)B1g as a ground state and hyperfine structure. The thermal stability and degradation of the ligands and their metal complexes were studied employing DTA and TG methods. The metal-free ligands and their copper(II) complexes were tested for their in vitro anticancer activity against human colon carcinoma (HT-29). The results showed that the synthesized copper(II) complexes exhibited higher anticancer activity than their free ligands. Of all the studied copper(II) complexes, the bromo-substituted complex 9b exhibited high anticancer activity at low micromolar inhibitory concentrations (IC50=0.58μM), compared to the other complexes and the free ligands.

Synthesis and characterization of some bi, tri and tetravalent transition metal complexes of N′-(furan-2-yl-methylene)-2-(p-tolylamino)acetohydrazide HL1 and N′-(thiophen-2-yl-methylene)-2-(p-tolylamino)acetohydrazide HL2

The tetradentate Schiff bases hydrazone ligands HL(1), HL(2) and their metal complexes have been prepared and characterized by analytical, spectral (IR, UV-vis, (1)H NMR and ESR), molar conductivity, magnetic and TGA measurements. The results show that all the metal complexes are non-electrolytes, except (2, 10 and 20) which have ionic nature. The ligands coordinate in keto-neutral form and act as bidentate or tridentate for all metal complexes, except complexes (4 and 12). The ligands react as monobasic tetradentate and tridentate for complexes (4 and 12), respectively. Octahedral/tetrahedral Co(II) and Ni(II), octahedral/square planar Cu(II), and octahedral Mn(II), Fe(III), Cr(III), Ru(III), Hf(IV) and Zr(IV)O geometries were proposed. The ESR spectra of copper complexes (12 and 14) indicate d(x2-y2) ground state with covalent bond character. The thermal decomposition and the types of crystallized water for some metal complexes were studied. The studied metal complexes are very weakly active against the tested microorganisms.

Cobalt(II), nickel(II), copper(II), zinc(II) and hafnium(IV) complexes of N′-(furan-3-ylmethylene)-2-(4-methoxyphenylamino)acetohydrazide

Cobalt(II), nickel(II), copper(II), zinc(II) and hafnium(IV) complexes of furan-2-carbaldehyde 4-methoxy-N-anilinoacetohydrazone were synthesized and characterized by elemental and thermal (TG and DTA) analyses, IR, UV-vis and (1)H NMR spectra as well as magnetic moment and molar conductivity. Mononuclear complexes are obtained with 1:1 molar ratio except complexes 3 and 9 which are obtained with 1:2 molar ratios. The IR spectra of ligand and metal complexes reveal various modes of chelation. The ligand behaves as a neutral bidentate one and coordination occurs via the carbonyl oxygen atom and azomethine nitrogen atom. The ligand behaves also as a monobasic tridentate one and coordination occurs through the enolic oxygen atom, azomethine nitrogen atom and the oxygen atom of furan ring. Moreover, the ligand behaves as a neutral tridentate and coordination occurs via the carbonyl oxygen, azomethine nitrogen and furan oxygen atoms as well as a monobasic bidentate and coordination occurs via the enolic oxygen atom and azomethine nitrogen atom. The electronic spectra and magnetic moment measurements reveal that all complexes possess octahedral geometry except the copper complex 10 possesses a square planar geometry. The thermal studies showed the type of water molecules involved in metal complexes as well as the thermal decomposition of some metal complexes.

First raw transition metal complexes of salicylidene and 2- hydroxy-1-naphthylidene-N-cyanoacetohydrazone

Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) complexes of salicylidene-N-cyano-acetohydrazone H2L1 and 2-hydroxy-l-naphthylidene-N-cyanoacetohydrazone H2L2 have been prepared in ethanolic solution and characterized by analytical, spectral, magnetic susceptibility, molar conductivity and TGA measurements. The analytical data show that all the complexes derived from H2L1 and H2L2 are formed in molar ratios 1M:2L, except the complexes of Mn(II), Co(II) and Cu(II) acetates of H2L2 and the complexes of Mn(II), Co(II) and Ni(II) acetates and CuCl2 of H2L1 are formed in 1:1 molar ratios. The conductance data show that all metal complexes are non-electrolytes. Electronic absorption spectra and magnetic susceptibility measurements proved that the prepared complexes have octahedral configuration except [Co(HL2)OAc] which has tetrahedral structure. The ligand field parameters were calculated for the Co(II) and Ni(II) complexes and the data show that the covalent character of the metal ligand sigma-bond is low. The ESR parameters of the Cu(II) complexes at room temperature were calculated. Thermal TGA for some solid complexes are reported.

Spectroscopic studies and thermal decomposition for (bis-(( E )-2-(4-ethylphenylimino)-1,2-diphenylethanone) Schiff base and its Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) complexes prepared by direct and template reactions

A new Schiff base (bis-((E)-2-(4-ethylphenylimino)-1,2-diphenylethanone) containing four active coordination centers (ONNO) and its metal complexes have been synthesized and characterized by elemental analyses, spectroscopic methods, molar conductance, thermal and magnetic measurements. The tetrahedral and square planar trinuclear Co(II), Ni(II) and Cu(II) complexes (1–3), respectively, have been prepared by direct reaction, while the template reaction gives octahedral complexes (4–8) with different stoichiometries 3:1, 2:1, 1:1 (M:L). The ESR spectra of solid copper (II) complexes in powder form showed an axial symmetry with 2B1g as a ground state. The thermal decomposition mechanisms of metal complexes were studied. All the thermal decomposition processes ended with the formation of metal oxide. The thermal study showed that the complexes with different solvents of crystallization exercise different types of interaction. The kinetic and thermodynamic parameters have been calculated.