New homodi-and heterotrinuclear metal complexes of Schiff base compartmental ligand: interaction studies of copper complexes with calf thymus DNA

The new homodinuclear complexes 1–4 of the type [LM^II ₂Cl₂], heterotrinuclear complexes 5 and 6 of the type [LM^II ₂Sn^IVCl₆] where M = Cu^II, Mn^II, Co^II, Ni^II and Cu^II and Ni^II, respectively have been synthesized and characterized by elemental analysis and various spectroscopic techniques. The homodinuclear complexes possess two different environments (N₂ and N₂O₂donor sets) for holding the metal ions. The metal ion in N₂ set exhibits square planar geometry with two chloride ions in the inner sphere but rhombic structure is found in tetradentate N₂O₂ Schiff base cavity while in heterotrinuclear complexes Sn^IV atom is in the octahedral environment. The interaction of complexes 1 and 5 with calf thymus DNA was carried out by absorption spectroscopy and cyclic voltammetry. The intrinsic binding constants (K _b ) of complex 1 and 5 were determined as 3.2 × 10³ M⁻¹ and 9.6 × 10³ M⁻¹, respectively suggesting that complex 5 binds more strongly to CT-DNA than complex 1. Fluorescence studies along with viscosity measurements have also been checked to authenticate the binding of metal complexes with DNA.     

Structure and luminescence of a nitrate-bridged heterotrinuclear Cu2-Pr complex with compartmental Schiff base ligand

A unique heterotrinuclear nitrate-bridged complex of hexanitrate praseodymium(III) and dicopper(II) compartmental species has been synthesized and characterized by X-ray single crystal structure analysis. The structure determination indicates that the dinuclear copper moiety undergoes a tilted deformation (with respect to the dicopper complex) upon connection to the lanthanide species via a rare nitrate bridge. The trinuclear species is highly fluorescent owing to the presence of praseodymium.     

Electrochemistry of transition metal complexes of Schiff base compartmental ligands

Summary The electrochemical behaviour of a series of mononuclear and dinuclear complexes of dioxouranium(VI), nickel(II) and copper(II) ions with the Schiff base, H₄fsalacen, derived from the condensation of 3-formylsalicylic acid and 1,2-diaminoethane, is reported.The potentially hexadentate compartmental ligand H₄fsalacen has an outer O₂O₂ and an inner N₂O₂ coordination site. The redox properties of the metal ions in these two different and adjacent chambers have been investigated and compared with those of the analogous complexes with the ligand H₄ aapen, obtained by reaction ofo-acetoacetylphenol and 1,2-diaminoethane.A preliminary report was presented at the 1st International Conference on the Chemistry and Technology of the Lanthanides and Actinides, Venice, 5 September, 1983, Italy.     

Electrochemical behaviour of the complexes of copper(II) with a Schiff base compartmental ligand

Summary The ethylenediamine Schiff base derivative ofo-acetoacetylphenol, H₄aapen, is a ligand able to form both mononuclear and dinuclear complexes with copper(II) ion. Mononuclear positional isomers can be obtained, having the copper in the O₂O₂ site and in the N₂O₂ site. The electrochemistry of these copper(II) complexes in dimethylsulfoxide shows that the two positional isomers are reduced at different potentials through an e.c.e. mechanism, in which a chemical reaction is coupled between two one-electron transfers, the N₂O₂ isomer being the less reducible. They also undergo complicated oxidation processes at high potentials, less significant in distinguishing the two isomers. The electrochemical behaviour of the dinuclear copper(II) complex parallels that of the two mononuclear isomers.     

Heterodinuclear Ln[bond]Na complexes with an asymmetrical macrocyclic compartmental Schiff base

Heterodinuclear lanthanide(III)-sodium(I) complexes [LnNa(L)(Cl)(2)(CH(3)OH)] (Ln=La[bond]Nd, Sm[bond]Lu), where H(2)L is a [1+1] asymmetric compartmental macrocyclic ligand containing a N(3)O(2) Schiff base and a O(3)O(2) crown-ether-like coordination site, have been prepared and characterized by IR, (1)H, (13)C, and (23)Na NMR spectroscopy, mass spectrometry, and electron microscopy. In the solid state, the lanthanide(III) ions coordinate the Schiff-base N(3)O(2) site, and the sodium ion occupies the O(3)O(2) crownlike cavity, as shown by the X-ray crystal structures of the Nd, Eu, Gd, and Yb derivatives. In these complexes, the lanthanide(III) ion is coordinated by two chlorine atoms in the trans position and by three nitrogen and two negatively charged phenol oxygen atoms of the Schiff base, and the ion is heptacoordinated with a pentagonal bipyramidal geometry. The sodium ion is coordinated by three etheric oxygen atoms and the two phenolic oxygens that act as a bridge. A methanol molecule is also coordinated in the apical position of the resulting pentagonal pyramidal polyhedron. A detailed (1)H and (13)C NMR study was carried out in CD(3)OD for both diamagnetic and paramagnetic heterodinuclear complexes [LnNa(L)(Cl)(2)(CH(3)OH)]. The complexes are also isostructural in solution, and their structures parallel those found in the solid state. Moreover, some significative distances determined in the solid state and in solution are comparable. Finally, the potential use of these complexes as molecular probes for the selective recognition of specific metal ions has been tested. In particular, their ability to act as shift reagents and the selectivity of the O(3)O(2) site towards Li(+), Ca(2+), and K(+) were investigated by (23)Na NMR spectroscopy.     

New Schiff base complexes of tetrachlorouranium

Summary Tetrachlorouranium complexes containing a Schiff base ligand, p-XC₆H₄NH=CHC₆H₄OH(L), derived from p-XC₆H₄NH₂ and salicylaldehyde, have been prepared. Atris complex was obtained when X=NO₂ andbis complexes for the other p-substituted Schiff bases when X=Cl, Br, OH and Me.     

Synthesis of chiral sulfonamide/Schiff base ligands

We report a facile two step synthesis of chiral ligands for bonding to transition metals. The ligands are easily prepared from trans-1,2-diaminocyclohexane by reaction with sulfonyl chlorides to give amino-sulfonamide compounds. These intermediates are then condensed with salicylaldehyde derivatives to provide sulfonamide/Schiff base compounds which represent a new class of chiral ligands.     

Amphiphilic Schiff base organogels: metal-ion-mediated chiral twists and chiral recognition

New amphiphilic gelators that contained both Schiff base and L-glutamide moieties, abbreviated as o-SLG and p-SLG, were synthesized and their self-assembly in various organic solvents in the absence and presence of metal ions was investigated. Gelation test revealed that o-SLG formed a thermotropic gel in many organic solvents, whilst p-SLG did not. When metal ions, such as Cu(2+), Zn(2+), Mg(2+), Ni(2+), were added, different behaviors were observed. The addition of Cu(2+) induced p-SLG to from an organogel. In the case of o-SLG, the addition of Cu(2+) and Mg(2+) ions maintained the gelating ability of the compound, whilst Zn(2+) and Ni(2+) ions destroyed the gel. In addition, the introduction of Cu(2+) ions caused the nanofiber gel to perform a chiral twist, whilst the Mg(2+) ions enhanced the fluorescence of the gel. More interestingly, the Mg(2+)-ion-mediated organogel showed differences in the fluorescence quenching by D- and L-tartaric acid, thus showing a chiral recognition ability.     

Coordination chemistry of Schiff base tin complexes

The most important results of extensive studies of tin metal complexes with Schiff base ligands are reviewed. A large number of inorganic compounds are known but still there is a need of new compounds to develop various efforts in different fields for biomedical applications.     

Transition metal complexes of heterocyclic Schiff base

Metal complexes of Schiff base derived from 2-furancarboxaldehyde and 2-aminobenzoic acid (HL) are reported and characterized based on elemental analyses, IR, ¹H NMR, UV-Vis, solid reflectance, magnetic moment, molar conductance and thermal analysis. The ligand dissociation as well as the metal-ligand stability constants have been calculated pH-metrically at 25°C and ionic strength μ=0.1 (1 M NaCl). The complexes are found to have the formulae [M(HL)₂](X)_n·yH₂O (where M=Fe(III) (X=Cl, n=3, y=4), Co(II) (X=Cl, n=y=2), Ni(II) (X=Cl, n=y=2), Cu(II) (X=Cl, n=y=2) and Zn(II) (X=AcO, n=y=2)) and [UO₂(L)₂]·2H₂O. The thermal behaviour of these chelates is studied and the activation thermodynamic parameters are calculated using Coats-Redfern method. The ligand and its metal complexes show a biological activity against some bacterial species.     

Schiff碱金属配合物的研究进展

简要介绍了Schiff碱金属配合物的发展历程、缩合反应机理、合成方法及其在材料、医药、催化等领域的研究、应用概况,并展望了其发展、应用前景.     

Bimetallic complexes of a potentially pentadentate,acyclic, symmetrical compartmental Schiff base ligand that provides suitable topology for an exogenous bridge

The binucleating ligand LH₃, 2,6-diformyl-p-cresol-bis(phenylthioacetyldrazone), a Schiff base condensation product of 2,6-diformyl-p-cresol and phenylthioacetyldrazide forms complexes of the [M₂ClL] type with Co^II, Ni^II and Cu^II ions, which were characterized by elemental analysis, magnetic susceptibility, electronic spectra, molar conductance, i.r., n.m.r., e.p.r., t.g. and FAB mass spectral measurements. Sub-normal magnetic moments indicate the operation of antiferromagnetic coupling between the metal centres. The ligand and its copper complex show a pronounced fungistatic activity.     

Binuclear organometallic ruthenium complexes of a Schiff base expanded porphyrin

The synthesis of binuclear organometallic ruthenium complexes of an expanded porphyrin-type macrocycle is reported; pyrrolic hydrogen bonding donors were found to interact with ancillary ligands in the primary coordination sphere and to stabilize coordinated dioxygen in an eta(2)-fashion.     

Schiff base tantalum(V) complexes

Summary Complexes of pentachlorotantalum with the Schiff bases: bis(vanillin)benzidine, bis(vanillin)-o-dianisidine, bis(acetylacetone)benzidine, bis(p-dimethylaminobenzaldehyde)-o-dianisidine, bis(anisaldehyde)-1, 3-propanediamine and bis(p-dimethylaminobenzaldehyde)-o-phenylenediamine have been prepared and characterized by molar conductance, decomposition temperature, elemental and t.g. analyses and i.r. spectral measurements. The conductances reveal that pentachlorotantalum (1 mole) interacts with all the ligands (1 mole), all five chloride ions thus forming simple adducts. A comparative study of the i.r. spectra of the parent ligands and their complexes allows the coordination sites to be ascertained. The studies show that tantalum(V) chloride prefers to form complexes of high coordination number.     

Pentanuclear tetra-decker luminescent lanthanide Schiff base complexes

Luminescent pentanuclear tetra-decker Ln(III) complexes [Eu5L4(OH)2(NO3)4(H2O)2].NO3.3H2O , [Nd5L4(OH)2(NO3)5MeOH].3MeOH.2H2O and [Eu5L4(CF3SO3)4(MeO)2(H2O)4].CF3SO3.H2O are formed from Ln(NO3)3.6H2O (Ln = Eu (1), Nd (2)) and Eu(CF3SO3)3, respectively (H2L = N,N'-bis(5-bromo-3-methoxysalicylidene)phenylene-1,2-diamine).     

Asymmetric sulfoxidation of prochiral sulfides using aminoalcohol derived chiral C3-symmetric trinuclear vanadium Schiff base complexes

A series of trimeric variants of the efficient and well known Bolm’s chiral vanadium salen catalysts are reported. These C₃-symmetric trinuclear chiral Schiff bases were synthesized by condensing a variety of trialdehydes with optically active aminoalcohols. The catalytic activity of the chiral vanadium complexes of these ligands was investigated for the enantioselective oxidation of prochiral sulfides using hydrogen peroxide as an oxidant. The procedure afforded the corresponding sulfoxide in good yield and the enantioselectivities were comparable to those obtained with the mononuclear complexes.     

Transition metal complexes of bidentate Schiff base ligands

New Schiff base ligands derived from vanillin (HL¹), 4-dimethylaminobenzaldehyde (HL²) and 3,5-di-t-butyl-4-hydroxybenzaldehyde (HL³) with N-(pyridyl)-3-methoxy-4-hydroxy-5-aminobenzylamine (2) and their copper(II), cobalt(II), nickel(II), oxovanadium(IV) and zinc(II) transition metal complexes have been synthesized and characterized by elemental analyses, electronic and i.r. spectra, molar conductance data and by 1H and ¹³C n.m.r. spectra. The results indicate that the ligands coordinate through azomethine nitrogen and phenolic oxygen to the metal ions. In like manner, it was found that the pyridine and amine nitrogen atoms are not coordinated to the metal ions. The ¹H and ¹³C n.m.r. spectral data confirmed the suggested structure for the Schiff base ligands, and the mass spectra results confirmed the proposed structure of the ligands. The antimicrobial activity properties of the ligands and their metal complexes have been studied.