Metallo-guanines and metallo-guanosines

Metallo-guanines of the type [M(G)₂·2H₂O] [M = Ni^II, Fe^II, Cu^II and UO₂ ^II; G = anionic guanine], [M(G)₂(GH)· H₂O] (M = Co^II and Mn^II; GH = neutral guanine), [Pd(G)₂]·2H₂O and [Zn(G)Cl]₂ have been isolated and characterised. Anionic guanine functions as a bidentate ligand and links through N(3) and N(9). E.p.r. data indicate that the Cu^II complex has a highly distorted octahedral structure. The magnetic susceptibility data suggest that the Co^II and Ni^II complexes possess pseudooctahedral geometry. Neutral guanines are probably unidentate and coordinate either through N(3) or N(9). The isolated guanosine complexes are of the types: [M(Gs)₂·H₂O] [M = Ni^II and Cu^II, Gs = anionic guanosine] [Pd(Gs)₂]·2H₂O and [UO₂(Gs)₂]. I.r. data indicate that guanosine also functions as a bidentate ligand, but coordinates through N(1) and C₂ — NH₂. The electronic absorption spectra of the complexes indicate that guanine is a stronger ligand than guanosine.     

Preparation and characterization of some transition metal complexes of benzoic acid hydrazones of 2-aminonicotinaldehyde

Summary Cu^II, Ni^II, Co^II, Zn^II and Pd^II complexes of tridentate Schiff base ligands derived from the condensation of benzoic acid hydrazides with 2-aminonicotinaldehyde have been prepared and characterized. For M=Cu, Ni, Co and Zn the complexes were formulated as [M(ligand)(H₂O)X] (X=Cl, Br), with a distorted octahedral geometry and tridentate Schiff base ligands. The Pd complexes were formulated as Pd(ligand)Cl₂, with square planar geometries and bidentate Schiff base ligands. The e.s.r. spectra of the Cu^II complexes are discussed.     

Synthesis and spectroscopic studies on 3-isonicotinamidorhodanine complexes of some bivalent metal ions

Summary 3-Isonicotinamido-rhodanine (HINRd) reacts with metal ions to yield complexes of the types M(INRd)OH·nH₂O (where M=Co^II, Ni^II, Zn^II or Cd^II and n=1 or 2), Cu(HINRd)X·2H₂O (where X=Cl or Br), Pd(HINRd)Cl₂ and Cd(HINRd)X₂·H₂O (where X=Cl or Br), depending on the metal salt used and the reaction conditions. The metal complexes have been characterized by elemental analysis, molar conductivities, molecular weights, magnetic susceptibility, visible, and i.r. studies. The i.r. spectra show that HINRd binds in a bidentate or monodentate manner. The spectral and magnetic studies suggest a tetrahedral arrangement for Co^II, octahedral for Ni^II and square-planar for Pd^II. HINRd behaves as a reducing agent towards Cu^II chloride or bromide forming diamagnetic Cu^I complexes.     

Metal complexes of ethylenediaminetetraacetamide

Summary A convenient synthesis of the ligand ethylenediaminetetraacetamide (L) is described, and a number of metal complexes of the general formula MLCl_n · xH₂O (Mⁿ⁺=Ca^II, Mn^II, Fe^II, Co^II, N^II, Cu^II, Zn^II, Mg^II, Ba^II, Cd^II, Hg^II and La^III) prepared. The deprotonated Cu(L-H)₂ · 2 H₂O complex has been characterised and the associated pK values determined. I.r., conductivity, magnetic susceptibility and electronic spectral data are discussed.     

Cobalt(II), nickel(II) and copper(II) complexes withN-cyano-N′-methyl-N″(2-[(5-methyl-1H-imidazol-4-yl)methylthio]ethyl)guanidine

Summary N-Cyano-N-methyl-N(2-[(5-methyl-1H-imidazol-4-yl)-methylthio] ethyl) guanidine cimetidine (CM), complexes with Co^II, Ni^II and Cu^II are described. The compounds are of stoichiometry [M(CM)₂]SO₄ · nH₂O [M = Co^II, Ni^II or Cu^II; n = 3,3 or 4, respectively], [M(CM)₂](ClO₄)₂ [M = Co^II or Ni^II], [M(CM)₂]Cl₂ · nH₂O [M=Co^II, Ni^II or Cu^II; n = 1, 2, or 2, respectively] and [Cu(CM)SO₄] · 2H₂O. The electronic spectra of the compounds in solid state, magnetic susceptibilities and i.r. and e.p.r. spectra were studied. Octahedral environments are proposed for the complexes: [M(CM)₂]SO₄·nH₂O, [M(CM)₂](ClO₄)₂, [Ni(CM)₂]Cl₂ · 2H₂O, [Cu(CM)₂]Cl₂ · 2H₂O and [Cu(CM)SO₄] · 2H₂O and a tetrahedral structure for [Co(CM)₂]Cl₂ · H₂O.     

Studies ono-hydroxyacetophenone-2-furoylhydrazone complexes of some 3d-bivalent metal ions

Summary Complexes ofo-hydroxyacetophenone-2-furoylhydrazone, H₂L, of the types M(H₂L)C1₂ · nH₂O [Mn = Co^II, n=0; Ni^II, n=2]; Cu(HL)Cl, M(HL)₂ [M = V^IVO, Co^II, Ni^II or Cu^II] and M(L)(H₂O)_n [M = Co^II or Ni^II, n=2; M = Cu^II, n=0] have been prepared and characterized by elemental analyses, molar conductance, magnetic susceptibility, visible, e.s.r. and i.r. spectral studies. The different modes of ligand chelation and the stereochemistry around the metal ions are discussed.     

Cobalt(II,III) and copper(II) complexes of 3-(2-furylidene) hydrazino-5,6-diphenyl-1,2,4-triazine

A new series of cobalt(II, III) and copper(II) complexes of 3-(2-furylidene) hydrazino-5,6-diphenyl-1,2,4-triazine (L) having formulae LM^IIX₂, L₂M^IIX₂ and LCo^IIIX₃, (X = Cl, OAc or ClO₄; M^II = Co^II or Cu^II) were isolated and characterized by elemental analyses, molar conductances, magnetic moments and i.r., electronic and e.s.r. spectral measurements. The i.r. spectra indicated that the ligand, L, behaves as a neutral bidentate towards divalent metal ions via a triazine-N, and azomethine-N, and acts as a tridentate towards cobalt(III) via the same two nitrogen atoms and the furan-O. The magnetic moments and electronic spectral data suggest a pseudo-tetrahedral geometry for [L₂Co]Cl₂, a diamagnetic tetragonally distorted octahedral geometry for [LCoCl₃], [LCo(OAc)₃] · 4H₂O and [LCo(H₂O)₃](ClO₄)₃ and a dimeric square pyramidal geometry for both [LCuCl₂] and [LCu(OAc)₂] · 2H₂O through bridged chloro and acetato ligands, respectively. The ligand field parameters (B, 10Dq and ) were evaluated from the electronic spectral data and magnetic moments and related to the bonding of the complexes. The X-band e.s.r. spectra showed three g values with large magnetic anisotropy for [L₂Co]Cl₂ in accordance with pseudo-tetrahedral Co^II complexes; axial pattern for [LCuCl₂], [LCu(OAc)₂] · 2H₂O and [L₂Cu(H₂O)₂](ClO₄)₂ with two g values and a signal due to M _s = ±2 transition for both chloro and acetato copper(II) complexes.     

Synthesis and antibacterial activity of metal complexes of ciprofloxacin

The interactions of ciprofloxacin (HCipro) with transition metals have been investigated. Two types of complexes, [M(Cipro)(OAc)(H₂O)₂] · 3H₂O (M = Mn^II, Co^II, Cu^II or Cd^II) and [M(Cipro)(OAc)] · 6H₂O (M = Ni^II or Zn^II), were obtained and characterized by physicochemical and spectroscopic methods. The i.r. spectra of the complexes suggest that the ciprofloxacin behaves as a monoanionic bidentate ligand. In vitro antibacterial activities of the HCipro and the complexes were tested.     

Synthesis spectroscopic and biological approach in the characterization of novel [N<Subscript>4</Subscript>] macrocyclic ligand and its transition metal complexes

A novel tetradentate nitrogen donor [N₄] macrocyclic ligand, i.e. 1,3,4,8,9,11-hexaaza-2,10-dithia-5,12-dioxo-7,14-diphenyl-cyclotetradecane (L), has been synthesized. Manganese(II),cobalt(II), nickel(II) and copper(II) complexes with this ligand have been prepared and subjected to elemental analyses, molar conductance measurements, magnetic susceptibility measurements, mass, ¹H-n.m.r. (Ligand), i.r., electronic, and e.p.r. spectral studies. On the basis of molar conductance the complexes may be formulated as [M(L)X₂] [where M = Mn^II, Co^II, Ni^II, and Co^II,and X = Cl⁻ & NO ₃ ⁻ ] due to their nonelectrolytic nature in dimethylformamide (DMF). All the complexes are of the high spin type and are six coordinated. On the basis of i.r., electronic and e.p.r. spectral studies an octahedral geometry has been assigned to Mn^II, and ^II, ^II, complexes, and tetragonal for copper(II) complexes. The antimicrobial activities of the ligand and its complexes, as growth inhibiting agents, have been screened in vitro against several species of bacteria and plant pathogenic fungi.     

Complexes of divalent oxovanadium,manganese, iron,cobalt, nickel and copper with the ligand derived from the reaction of 2-aminopyridine and acetylacetone

Summary 2-Aminopyridine reacts with acetylacetone in the presence of VO^II, Mn^II, Fe^II, Co^II, Ni^II, and Cu^II metal salts to give complexes of the type [VO(Ap₂ac)₂X]X and [M(Ap₂ac)₂X₂] where (Ap₂ac) is the ligand formedin situ. The complexes are characterised as distorted octahedral by analyses, conductance, molecular weight, magnetic, electronic and i.r. spectral studies. The i.r. studies reveal that two molecules of aminopyridine are joined by a molecule of acetylacetone through a three carbon atom bridge and that the ligand coordinates through the azomethine and imino nitrogen atoms, whereas pyridine does not take part in coordination. The electronic spectra have been interpreted and tentative assignments are made. In the far i.r. spectra, various metal ligand vibrations are observed and discussed. Attempts to carry out electrophilic substitutions in the complexes failed.     

Cobalt(II), nickel(II) and copper(II) complexes of 4-(sulfonylazido)phenylazopyrazolones

Transition metal complexes of Co^II, Ni^II and Cu^II with 4-(4-azidosulfophenylazo)-5-phenyl-3,4-dihydro-2H-pyrazol-3-oneHL¹, 4-(4-azidosulfophenylazo)-5-methyl-2-phenyl-3,4-dihydro-2H-pyrazol-3-one HL² and 4-(3-azidosulfo-6-methoxyphenylazo)-5-methyl-2-phenyl-3,4-dihydro-2H-pyrazol-3-one HL³ were prepared and characterized by elemental analyses, molar conductances and magnetic susceptibilities and by i.r., electronic and e.s.r. spectral measurements as well as thermal (d.t.a and t.g.a.) analysis. The i.r. spectra indicate that HL acts as a bidentate ligand coordinating via the azo and enolic-oxygen linkages. The electronic spectral data and magnetic moments suggest a tetragonally distorted octahedral geometry for the complexes having the formula ML₂·2H₂O, (M = Co^II, Ni^II and Cu^II), square pyramidal geometry for CuL ₂ ³ H₂O and tetrahedral geometry for CoL ₂ ³ . The X-band e.s.r. spectra of the copper(II) complexes reveal anaxial symmetry for both CuL ₂ ² 2H₂O and CuL ₂ ³ H₂O while CuL ₂ ¹ O is isotropic in the solid state at room temperature. The d.t.a. curves show two exothermic peaks for all three complexes CoL ₂ ³ ,NiL ₂ ³ 2H₂O and CuL ₂ ³ H₂O and one endothermic peak for the latter two aqua complexes.     

Preparation, structural characterization and vibrational spectroscopic studies of transition metal complexes of singly- and doubly-deprotonated N-methyl-2-thiooxamic acid

Summary Synthetic procedures are described that allow access to the new monomeric complexes [M(HA)₂(H₂O)₂]·2H₂O (M = Mn or Co), [M(HA)₂(H₂O)₂] (M = Fe, Ni or Zn) and [Cu(HA)₂], and to the polymeric compounds [MA(H₂O)] _n (M = Mn, Co, Ni or Zn) and [CuA] _n , where H₂A = N-methyl-2-thiooxamic acid. The X-ray crystal structure of [Mn(HA)₂(H₂O)₂]·2H₂O reveals a trans, cis, cis octahedral geometry around the metal ion. The singlydeprotonated ligand behaves as a bidentate chelate with ligated atoms being the neutral thioamide sulfur and one of the carboxylate oxygens. The complexes were characterized by elemental analyses, conductivity measurements, X-ray powder patterns, magnetic susceptibilities and spectroscopic (e.s.r., ligand field, i.r., far-i.r., Raman) studies. The vibrational analysis of the complexes is presented using OH/OD, NH/ND, CH₃/CD₃ and metal isotopic substitutions. All data are discussed in terms of the nature of bonding in conjunction with known or assigned structures. The dianion A^2– acts as a bis-bidentate O,N/O,S bridging ligand yielding highly symmetrical squares planar (Cu^II) and octahedral (Mn^II, Co^II, Ni^II and Zn^II) polymeric compounds.Dedicated to the memory of Professor Andreas G. Galinos     

Studies on 2-acetylthiophene-2-furoylhydrazone complexes of 3d-bivalent metal ions

Summary Metal(II) complexes of 2-acetylthiophene-2-furoylhydrazone (HL) of the types [VO(HL)SO₄], [Cu(HL)₂Cl₂(H₂O)], [M(HL)₂Cl₂] [M=Co^II, Ni^II, or Zn^II] and [ML₂(H₂O)₂] [M=Co^II, Ni^II, Cu^II or Zn^II] have been prepared and characterized on the basis of elemental analyses, molar conductance, magnetic susceptibility, visible, e.s.r. and i.r. spectral studies. The bonding and stereochemistry of the complexes are discussed.     

Structural studies of 4-benzamido-1-o-aminoacetophenone-3-thiosemicarbazone complexes

Summary Complexes of Cu^II, Ni^II, Co^II, Zn^II, Cd^II and Hg^II with 4-benzamido-1-o-aminoacetophenone-3-thiosemicarbazone (H₂BATS) are reported and have been characterized by elemental analyses, molar conductivities, magnetic moments, spectral (visible, i.r.) and thermal (d.t.a., t.g., d.t.g.) measurements. I.r. spectra show that H₂BATS behaves as a dianionic, monoanionic or neutral tetradentate ligand or as a monoanionic tridentate ligand. [Cu₂(H₂BATS)Cl₂]·2H₂O and [Cu₂(H₂BATS)Ac₂]·2H₂O complexes are diamagnetic while [Co(HBATS)OH]·2H₂O and [Ni(HBATS)OH]·2H₂O are octahedral. All the complexes are non-electrolytes. Generally, the solid metal acetate complexes have a unique decomposition exotherm profile which can be used as a rapid and sensitive tool for the detection of acetate-containing complexes.     

Cobalt(II), nickel(II) and copper(II) complexes of 5-(2-carboxyphenylazo)-2-thiohydantoin

A new series of hexacoordinate cobalt(II), nickel(II) and copper(II) complexes of 5-(2-carboxyphenylazo)-2-thiohydantoin HL having formulae [LM(OAc)(H₂O)₂] · nH₂O (M = Co^II, Cu^II and Ni^II), [LMCl(H₂O)₂] · nH₂O (M = Co^II and Ni^II), [LCuCl(H₂O)]₂ · 2H₂O, [LCu(H₂O)₃](ClO₄) and [LCu(HSO₄)(H₂O)₂] were isolated and characterized by elemental analyses, molar conductivities and magnetic susceptibilities, and by i.r., electronic and e.s.r. spectral measurements, as well as by thermal (t.g. and d.t.g.) analyses. The i.r. spectra indicate that the ligand HL behaves as a monobasic tridentate towards the three divalent metal ions via an azo-N, carboxylate-O and thiohydantoin-O atom. The magnetic moments and electronic spectral data suggest an octahedral geometry for Co^II complexes, distorted octahedral geometry for both Ni^II and Cu^II complexes with a dimeric structure for [LCuCl(H₂O)]₂ · 2H₂O through bridged chloro ligands. The X-band e.s.r. spectra reveal an axial symmetry for the copper(II) complexes with unsymmetrical M_s = ± 1 signal and G-parameter less than four for the dimeric [LCuCl(H₂O)]₂ · 2H₂O. The thermogravimetry (t.g. and d.t.g.) of some complexes were studied; the order and kinetic parameters of their thermal degradation were determined by applying Coats–Redfern method and discussed.     

Ligational behaviour of a tetradentate NONS donor ligand towards some transition metal ions

Summary The synthesis and characterization of Cr^II, Mn^II, Fe^II, Co^II, Ni^II, Pd^II, Cu^II, Zn^II, Cd^II and UO ₂ ²⁺ complexes of 1-meotinoyl-4-phenyl-3-thiosemicarbazide (H₂NTS) are reported. I.r. spectral data show that the ligand behaves in a bidentate and/or tetradentate manner. An octahedral structure is proposed for the Cr^II, Fe^II and Ni^II complexes; a tetrahedral structure for the Mn^II, Co^II and Cu(NTS)·2H₂O complexes; and a square planar structure for the Pd^II and Cu(HNTS)Cl·H₂O complexes. The i.r. data suggest that the Fe^II complex contains a hydroxo bridge.     

2-Aminoacetophenone-2-thenoylhydrazone complexes of bivalent 3d metal ions

Summary 2-Aminoacetophenone-2-thenoylhydrazone, Haath, C₄H₃SC(O)NHN=C(Me)C₆H₄NH₂-o, forms complexes with metal(II) salts of empirical compositions [VO(Haath)₂SO₄], [M(Haath)₂Cl₂] [M=Co^II, Ni^II, Cu^II or Zn^II] and [M(aath)₂] [M=V^IVO, Co^II, Ni^II, Cu^II or Zn^II] which have been characterized by elemental analyses, molar conductance, magnetic susceptibility, electronic, e.s.r., i.r. and n.m.r. (¹H and¹³C) spectral studies. X-ray and electron diffraction patterns have been obtained in order to elucidate the structure of the Cu^II complexes. Photoacoustic spectra of powder Ni^II complexes have been recorded and interpreted in the light of u.v./vis. spectra.     

Synthesis, Characterization and Antibacterial Activity of Some Transition Metal cis-3,7-dimethyl-2,6-octadiensemicarbazone Complexes

The synthesis and characterization of some transition metal cis-3,7-dimethyl-2,6-octadiensemicarbazone (CDOSC) complexes are reported. The ligand CDOSC yields: [ML₂ Cl₂] and [ML₂ Cl₂] Cl type complexes, where M = Cr^III, Mn^II, Fe^III, Co^II, Ni^II, Cu^II, Zn^II, Cd^II and Hg^II, L = CDOSC. Structures of the complexes were determined using elemental analysis, molar conductivity, magnetic measurements, i.r. and electronic, as well as n.m.r spectra. CDOSC acts as a bidentate ligand in all the complexes. All the newly synthesized metal complexes, as well as the ligand, were screened for their antibacterial activity. All the complexes exhibit strong inhibitory action against Gram (+) bacteria Staphylococcus aureus and Gram (−) bacteria Escherichia coli. The antibacterial activities of the complexes are stronger than those of the ligand CDOSC itself.     

Metal complexes of tetramethylethylenediaminetetraacetate

Summary A number of metal complexes of the ligand tetramethylethylenediaminetetraacetate [Edta(OMe)₄ = L] have been characterised. The complexes may be formulated MLCl₂ · xH₂O where M²⁺ = Mn^II, Fe^II, Co^II, Ni^II, Cu^II, Cd^II, Hg^II and Sn^II. I.r., conductivity, magnetic susceptibility and electronic spectral data are discussed.     

Metal complexes of the flavonoid quercetin: antibacterial properties

Two types of complexes were obtained when quercetin (L) was reacted with metal ions in EtOH. The compounds [M(L)Cl₂(H₂O)₂] (M = Mn^II or Co^II) and the semi-oxidized complexes [M(L)₂CL₂] · 2H₂O (M = Cd^II or Hg^II) were characterized by elemental analysis., conductivity and magnetic susceptibility measurements, i.r., u.v.–vis. and e.p.r. spectroscopy. The (C=O) stretching mode located on the C ring of the ligand and the complexes remains in the same range, showing that this oxygen atom does not participate in coordination to the metal ions. Magnetic susceptibilities and e.p.r. spectra of powdered samples indicated that the monomeric form of the complexes in the solid state, and the paramagnetic nature of the Cd^II and Hg^II complexes is attributable to the semiquinone character of the ligand. The antibacterial activity of the metal complexes were tested against five bacterial strains and compared with penicillin activity.