Transition metal(II) complexes of (E)-cinnamoylferrocene (S)-methylcarbodithioylhydrazone

A new organometallic ligand, (E)-cinnamoylferrocene (S)-methylcarbodithioylhydrazone (HCfmc) and six transition metal(II) complexes thereof M(Cfmc)2·nH2O (M=Co2+, Ni2+, Cu2+, Zn2+, Cd2+ and Hg2+; n=0–2) have been prepared and characterized by elemetal analyses, i.r., u.v., 1H-n.m.r. spectra, electrochemical properties, fluorescence spectra and molar conductances. The HCfmc ligand acts as a bidentate donor, coordinating to the metal ions via nitrogen and sulfur atoms with a trans-configuration.     

Antitumor activity of transition metal(II) complexes with all- trans retinoic acid

Five complexes of transition metals with all-trans retinoic acid (HRA) have been prepared and characterized by elemental analysis, molar conductance, t.g.–d.t.a, i.r., and u.v.-vis. spectroscopy, and 1H-n.m.r. spectrometry. The general formula of these complexes is ML2 ·nH2O where L=RA, M=MnII, CoII, NiII, CuII, ZnII, and n=3 or 4. They have been studied for their antitumour activity against human bladder cancer line EJ (EJ cells) with respect to proliferation, induce differentiation, P21 and mutation P53 expressions in vitro.     

Synthesis,electrochemical and an e.s.r study of heterodinuclear MIIZnII (M = Cu,Ni, and VO) complexes of asymmetric macrocyclic ligands made from 2,6-diacetyl-4-methylphenol

A series of heterodinuclear complexes, [MZnL][ClO4)2· nH2O (M = Cu, Ni, and VO) where L is a dinucleating Schiff base ligand derived from the condensation of 2,6-diacetyl-4-methylphenol (1mole), with ethylenediamine (1mole), 1,2-diaminopropane (1mole), or 1,3-diaminopropane (1mole) have been synthesized and evaluated. The complexes exhibit a single one-electron redox couple as anticipated. The e.s.r spectra for the CuZn complex shows an isotropic signal and the frozen glass spectra of VOZn complex is characterized by two sets of eight lines.     

Synthesis,structure and antitumor activities of a new macrocyclic ligand with four neutral pendent groups: 1,4,7,10-tetrakisbenzyl-1,4,7,10-tetraazacyclododecane (L) and its Co,Ni and Cu complexes

A new macrocyclic ligand, 1,4,7,10-tetrakisbenzyl-1,4,7,10-tetraazacyclododecane (L) and its three new divalent metal complexes of general formula: M(NO₃)₂(L)nH2O [M = Co(1), Ni(2), n = 0; M = Cu(3), n = 1.5] have been synthesized and characterized by elemental analysis, i.r., EI mass spectra and molecular conductance. Complex (2) has been characterized by X-ray diffraction. In complex (2), the central Ni^II atom coordinatively bonds to four nitrogen atoms of the macrocyclic ligand and two oxygen atoms of nitrate anion, to form a distorted octahedron. X-ray diffraction indicated that the bonds Ni–N(1), Ni–N(2), Ni–N(3) and Ni–N(4) are of almost equal length, i.e. 2.11(1), 2.12(1), 2.10(1) and 2.17(1)Å, respectively. Bond lengths of Ni–O(1) and Ni– O(2) are 2.11(1) and 2.10(1)Å. Preliminary pharmacological tests show that these complexes have high antitumor activity towards HL-60 tumor cell lines.     

Homo and heteronuclear complexes of dioxime ligands

The mononuclear fragments [Cu(HDopn)(OH)2]+ and [Cu(HPopn)(OH)2]+, [H2Dopn=3,3-(trimethylene- dinitrilo)-dibutan-2–one dioximate and H2Popn, = 3, 3-(phenylenedinitrilo)-dibutan-2–one dioximate] were used to prepare four binuclear complexes [(OH2)Cu (Dopn)Cu(ditn)]2+, [(OH2)Cu(Dopn)Ni(ditn)(H2O)]2+ (ditn=diethylenetriamine) and [(OH2)Cu(Popn)Cu(L) (H2O)]2+ (L=2,2-bipyridine or 1,10–phenanthroline). Two trinuclear complexes, [{Cu(Popn)(OH2)}2M (H2O)n]2+ (when M=CuII, n=1; M=ZnII, n= 2), have been synthesised and characterised by elemental analyses, f.a.b. mass, i.r., electronic, e.s.r. spectroscopy and variable temperature (5–300K) magnetic susceptibility measurements. A strong antiferromagnetic interaction (J=–545cm–1 to –700cm–1) has been found for the binuclear copper(II) complexes. The X-band e.s.r. spectra of these complexes at 300K and for trinuclear complexes at 120K indicate square-pyramidal geometry for the copper centres with a (dx2–y2)1 ground state. The binuclear complex of copper(II)–nickel(II) centres with antiferromagnetic interaction (J=–107 cm–1) is described, and moderately strong zero-field splitting within the quartet state leads to Kramers doublet, as indicated by X-band e.s.r. spectra of this complex. The trinuclear copper(II) complex with an antiferromagnetic interaction (J= –350cm–1) is also described. The heterometallic trinuclear copper(II)–zinc(II)–copper(II) system shows a very weak interaction (J–1cm–1).     

Synthesis, spectral characterization, solution equilibria, in vitro antibacterial and cytotoxic activities of Cu(II), Ni(II), Mn(II), Co(II) and Zn(II) complexes with Schiff base derived from 5-bromosalicylaldehyde and 2-aminomethylthiophene

Schiff base namely 2-aminomethylthiophenyl-4-bromosalicylaldehyde (ATS)(4-bromo-2-(thiophen-2-yl-imino)methylphenol) and its metal complexes have been synthesized and characterized by elemental analyses, IR, 1H NMR, solid reflectance, magnetic moment, molar conductance, mass spectra, ESR and thermal analysis (TGA). The analytical data of the complexes show the formation of 1:2 [M:L] ratio of the formula [ML2], where M represents Ni(II), Zn(II) and Cu(II) ions, while L represents the deprotonated Schiff base. IR spectra show that ATS is coordinated to the metal ions in a bidentate manner through azomethine-N and phenolic-oxygen groups. The ligand and their metal chelates have been screened for their antimicrobial activities using the disc diffusion method against the selected bacteria. A cytotoxicity of the compounds against colon (HCT116) and larynx (HEP2) cancer cells have been studied. Protonation constants of (ATS) ligand and stability constants of its Cu2+, Co2+, Mn2+, Zn2+ and Ni2+ complexes were determined by potentiometric titration method in 50% (v/v) DMSO-water solution at ionic strength of 0.1 M NaNO3.     

Synthesis,crystal structure and magnetic properties of a series of polymeric lanthanoid–copper complexes [Ln2Cu3{O(CH2−CO2)2}6]·nH2O (Ln=La,Nd, n=9; Ln=Er,n=6)

The reaction of diglycolic acid, O(CH2CO2H)2, with Cu(NO3)2·2H2O and lanthanoid nitrate hydrate produces a series of novel Ln–Cu mixed metal complexes, [Ln2Cu3{O(CH2CO2)2}6]·nH2O (Ln=La, Nd, n=9; Ln=Er, n=6), which have been characterized by elemental analysis, i.r. spectroscopy, magnetic measurements and X-ray crystallography. The Ln3+ and Cu2+ ions are connected by the carboxylate groups of the ligands, resulting in the formation of a complicated network.     

Synthesis, characterization and thermal studies on metal complexes of new azo compounds derived from sulfa drugs

Four new azo ligands, L1 and HL2-4, of sulfa drugs have been prepared and characterized. [MX(2)(L1)(H(2)O)(m)].nH(2)O; [(MX(2))(2)(HL2 or HL3)(H(2)O)(m)].nH(2)O and [M(2)X(3)(L4)(H(2)O)].nH(2)O; M=Co(II), Ni(II) and Cu(II) (X=Cl) and Zn(II) (X=AcO); m=0-4 and n=0-3, complexes were prepared. Elemental and thermal analyses (TGA and DTA), IR, solid reflectance spectra, magnetic moment and molar conductance measurements have accomplished characterization of the complexes. The IR data reveal that HL1 and HL2-3 ligands behave as a bidentate neutral ligands while HL4 ligand behaves as a bidentate monoionic ligand. They coordinated to the metal ions via the carbonyl O, enolic sulfonamide S(O)OH, pyrazole or thiazole N and azo N groups. The molar conductance data reveal that the chelates are non-electrolytes. From the solid reflectance spectra and magnetic moment data, the complexes were found to have octahedral, tetrahedral and square planar geometrical structures. The thermal behaviour of these chelates shows that the water molecules (hydrated and coordinated) and the anions are removed in a successive two steps followed immediately by decomposition of the ligand in the subsequent steps. The activation thermodynamic parameters, such as, E*, DeltaH*, DeltaS* and DeltaG* are calculated from the TG curves applying Coats-Redfern method.     

Transition metal complexes of 2-formylthiophene S-methyldithiocarbazate

Transition metal complexes of 2-formylthiophene S-methyldithiocarbazate have been synthesized and characterized. Analytical data show that the complexes are of the type [ML3], where M = Fe3+, and [ML2], where M=Ni2+, Cu2+ or Zn2+. The i.r. spectra suggest coordination to the metal through the azomethine nitrogen and thiolate sulfur. The magnetic and spectroscopic data indicate a square planar geometry for the complexes, except for the Fe3+ complex, which is octahedral. The e.s.r. parameters are indicative of a square planar N2S2 system for the Cu2+ complex.     

Potentiometric, spectroscopic and thermal studies on the metal chelates of 1-(2-thiazolylazo)-2-naphthalenol

The synthesis and characterization of Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Pd(II) and UO2(II) chelates of 1-(2-thiazolylazo)-2-naphthalenol (TAN) were reported. The dissociation constants of the ligand and the stability constants of the metal complexes were calculated pH-metrically at 25 degrees C and 0.1 M ionic strength. The solid complexes were characterized by elemental and thermal analyses, molar conductance, IR, magnetic and diffuse reflectance spectra. The complexes were found to have the formulae [M(L)2] for M = Mn(II), Co(II), Ni(II), Zn(II) and Cd(II); [M(L)X].nH2O for M = Cu(II) (X = AcO, n = 3), Pd(II) (X = Cl, n = 0) and UO2(II) (X = NO3, n = 0), and [Fe(L)Cl2(H2O)].2H2O. The molar conductance data reveal that the chelates are non-electrolytes. IR spectra show that the ligand is coordinated to the metal ions in a terdentate manner with ONN donor sites of the naphthyl OH, azo N and thiazole N. An octahedral structure is proposed for Mn(II), Fe(III), Co(II), Ni(II), Zn(II), Cd(II) and UO2(II) complexes and a square planar structure for Cu(II) and Pd(II) complexes. The thermal behaviour of these chelates shows that water molecules (coordinated and hydrated) and anions are removed in two successive steps followed immediately by decomposition of the ligand molecule in the subsequent steps. The relative thermal stability of the chelates is evaluated. The final decomposition products are found to be the corresponding metal oxides. The thermodynamic activation parameters, such as E*, delta H*, delta S* and delta G* are calculated from the TG curves.     

Transfer of a quadridentate N2S2 ligand from M2+ (M=Cr,Mn, Fe,Co or Ni) to Cu2+: Unexpected reactivities of bimetallic intermediates

A series of complexes of stoichiometry [MX2(dipyS)] {dipyS = bis(2–picolyl)-1,3–dithiopropane); M=Cr, Mn, Fe, Co, Ni, X=Cl; M=Ni or Cu, X=NO3} and [VOCl(dipyS)]Cl have been prepared and characterised, including the X-ray crystal structure of [Ni(ONO2)2(dipyS)]. The kinetics of the transfer of dipyS from these complexes (M=Cr, Mn, Fe, Co or Ni) to Cu2+, to form [Cu(dipyS)]2+, have been studied in MeOH. For M=Ni, the kinetics are consistent with a mechanism involving rate-limiting dissociation of the initial pyridyl—M bond. Subsequent binding of Cu2+ to the pendant pyridyl-residue (or binding Cl– to the vacant site on M) is followed by the complete transfer of dipyS from M to Cu. For M=Cr, Mn or Co, the same mechanism is believed to operate, but in these cases intermediates in the dipyS transfer to Cu2+ have been detected spectroscopically. Evidence is presented that these intermediates have Cu2+ bound to a pendant pyridyl-group on [MCl2(dipyS)] and that the subsequent complete transfer of dipyS involves rate-limiting dissociation of a M—S bond. For M=Fe, e.p.r. spectroscopy shows that the complex is a dimer in solution. However, the transfer reaction with Cu2+ involves an analogous intermediate to that with M=Cr, Mn or Co, but only at high concentrations of Cu2+. Unexpectedly, the binding of Cu2+ inhibits the transfer of dipyS from Fe to Cu. The electronic factors which give rise to this behaviour are discussed.     

杂多阴离子的相转移化学 Ⅰ.取代的Keggin及Dawson结构杂多阴离子在非极性溶剂中的溶剂化行为研究

利用四庚基溴化铵将Keggin结构的杂多阴离子ZW~1~1O~3~9M(H~2O)^n^-(Z=Si,Ge,P,M=Ni^2^+,Cu^2^+,Cr^3^+,Co^2^+,n=4～6)和Dawson结构的杂多阴离子P~2W~1~7O~6~1M(H~2O)^n^-(M=Ni^2^+,Cu^2^+,Cr^3^+,Co^2^+,n=7,8) 从水溶液中转移至非极性溶剂(苯或甲苯)中,并观察到在水溶液中难以进行的配位水的脱去反应,形成配位不饱和的杂多阴离子.当加入Lewis碱如丙酮,吡啶等,可迅速恢复饱和配位,其电子吸收光谱也相应变化,基本恢复到配位饱和时的数值,有ESR信号.实验表明,在非极性溶剂中,配体之间相互进行的取代反应,吡啶的配位能力最强, 发生了取代反应ZW~1~1O~3~9M(L)^n^-+Py→ZW~1~1O~3~9M(Py)^n^-+L(L=丙酮,乙腈等).同时我们也研究了温度,杂多阴离子浓度,惰性气体流量对杂多阴离子在非极性溶剂中的溶剂化行为的影响,得到了相转移的一般规律,为杂多阴离子在非极性溶剂中的催化研究提供了理论依据     

Template synthesis and spectroscopic studies of highly conjugated tetraiminetetraamide macrocyclic complexes from 1,2-diphenylethane-1,2-dione dihydrazone

A new class of tetraiminetetraamide macrocyclic (Ph4[20]tetraene, N8O4, and Ph6[20]tetraene, N8O4) complexes have been prepared through the metal ion controlled reaction of 1,2-diphenylethane-1,2-dione dihydrazone (DPEDDH) with succinic acid [ML1X2] or phthalic acid [ML2X2] [M=Mn, Co, Ni, Cu or Zn; X=Cl or NO3]. The structures of the complexes have been elucidated on the basis of i.r, 1H-n.m.r, e.p.r. and electronic spectral data and conductance, as well as magnetic, properties. An octahedral geometry is assigned for all the complexes, involving coordination of the all-imine nitrogens.     

Structure investigation, spectral, thermal, X-ray and mass characterization of piroxicam and its metal complexes

[M(H2L)2](A)2.yH2O (where H2L: neutral piroxicam (Pir), A: Cl- in case of Ni(II) or acetate anion in case of Cu(II) and Zn(II) ions and y=0-2.5) and [M(H2L)3](A)z.yH2O (A: SO4(2-) in case of Fe(II) ion (z=1) or Cl(-) in case of Fe(III) (z=3) and Co(II) ions (z=2) and y=1-4) chelates are prepared and characterized using elemental analyses, IR, magnetic and electronic reflectance measurements, mass spectra and thermal analyses. IR spectra reveal that Pir behaves a neutral bidentate ligand coordinated to the metal ions through the pyridyl-N and carbonyl-O of the amide moiety. The reflectance and magnetic moment measurements reveal that these chelates have tetrahedral, square planar and octahedral geometrical structures. Mass spectra and thermal analyses are also used to confirm the proposed formulae and the possible fragments resulted from fragmentation of Pir and its chelates. The thermal behaviour of the chelates (TGA and DTA) are discussed in detail and the thermal stability of the anhydrous chelates follow the order Ni(II) congruent with Cu(II) Fe(II)相似文献   

Uranyl binary and ternary chelates of tenoxicam Synthesis, spectroscopic and thermal characterization of ternary chelates of tenoxicam and alanine with transition metals

Ternary Fe(III), Co(II), Ni(II), Cu(II), Zn(II) and UO(2)(II) chelates with tenoxicam (Ten) drug (H(2)L(1)) and dl-alanine (Ala) (HL(2)) and also the binary UO(2)(II) chelate with Ten were studied. The structures of the chelates were elucidated using elemental, molar conductance, magnetic moment, IR, diffused reflectance and thermal analyses. UO(2)(II) binary chelate was isolated in 1:2 ratio with the formula [UO(2)(H(2)L)(2)](NO(3))(2). The ternary chelates were isolated in 1:1:1 (M:H(2)L(1):L(2)) ratios and have the general formulae [M(H(2)L(1))(L(2))(Cl)(n)(H(2)O)(m)].yH(2)O (M=Fe(III) (n=2, m=0, y=2), Co(II) (n=1, m=1, y=2) and Ni(II) (n=1, m=1, y=3)); [M(H(2)L(1))(L(2))](X)(z).yH(2)O (M=Cu(II) (X=AcO, z=1, y=0), Zn(II) (X=AcO, z=1, y=3) and UO(2)(II) (X=NO(3), z=1, y=2)). IR spectra reveal that Ten behaves as a neutral bidentate ligand coordinated to the metal ions via the pyridine-N and carbonyl-O groups, while Ala behaves as a uninegatively bidentate ligand coordinated to the metal ions via the deprotonated carboxylate-O and amino-N. The magnetic and reflectance spectral data confirm that all the chelates have octahedral geometry except Cu(II) and Zn(II) chelates have tetrahedral structures. Thermal decomposition of the chelates was discussed in relation to structure and different thermodynamic parameters of the decomposition stages were evaluated.     

Mixed ligand complexes of bis(phenylimine) Schiff base ligands incorporating pyridinium moiety Synthesis, characterization and antibacterial activity

The synthesis and structural characterization of mixed ligand complexes derived from 2,6-pyridinedicarboxaldehydebis(o-hydroxyphenylimine), 2,6-pyridinedicarboxaldehydebis(p-hydroxyphenylimine) (1(ry) ligands) and 2-aminopyridne (2(ry) ligand) are reported. The ligands and their transition metal complexes were characterized on the bases of their elemental analyses, IR, solid reflectance, magnetic moment, molar conductance and thermal analysis (TGA). The mixed ligand complexes are formed in the 1:1:1 (M:L(1) or L(2):L') ratio as found from the elemental analyses and found to have the formulae [MX(2)(L(1) or L(2))(L')].nH(2)O where M = Co(II), Ni(II), Cu(II) and Zn(II), L(1) = 2,6-pyridinedicarboxaldehydebis(p-hydroxyphenylimine), L(2) = 2,6-pyridine dicarboxaldehydebis(o-hydroxyphenylimine), L' = 2-aminopyridine, X = Cl(-) in case of Cu(II) complex and Br(-) in case of Co(II), Ni(II) and Zn(II) complexes and y = 0-3. The molar conductance data reveal that the chelates are non-electrolytes. IR spectra show that the Schiff bases are coordinated to the metal ions in a terdentate manner with NNN donor sites of the pyridine-N and two azomethine-N. While 2-aminopyridine coordinated to the metal ions via its pyridine-N. Magnetic and solid reflectance spectra are used to infer the coordinating capacity of the ligand and the geometrical structure of these complexes are found to be octahedral. The thermal behaviour of these chelates shows that the hydrated water molecules and the anions are removed in a successive two steps followed immediately by decomposition of the ligands (L(1), L(2) and L') in the subsequent steps. The activation thermodynamic parameters, such as, E*, DeltaH*, DeltaS* and DeltaG* are calculated from the TG curves and discussed. The ligands and their metal chelates have been screened for their antimicrobial activities and the findings have been reported, explained and compared with some known antibiotics.     

The preparation and characterization of some new nickel(II), copper(II), zinc(II) and cadmium(II) complexes of the pyrrole-2-carboxaldehyde Schiff bases ofS-alkyl esters of dithiocarbazic acid

Summary New complexes of general formulae [Ni(HL)₂], [ML]·H₂O and [Cu(HL)X] (H₂L = pyrrole-2-aldehyde Schiff bases ofS-methyl- andS-benzyldithiocarbazates; X = Cl or Br; M = Ni^II, Cu^II, Zn^II or Cd^II) were prepared and characterized by a variety of physicochemical techniques. The Schiff bases coordinate as NS bidentate chelating agents in [Ni(HL)₂] and [Cu(HL)X], and as tridentate NNS chelates in [ML] (M = Ni^II, Cu^II, Zn^II or Cd^II). Both the [Ni(HL)₂] and [NiL] complexes are diamagnetic and square-planar. Based on magnetic and spectroscopic evidence, thiolate sulphur-bridged dimeric square-planar structures are assigned to the [Cu(HL)X] and [ML] (M = Ni^II or Cu^II) complexes. The complexes ML (M = Zn^II or Cd^II) are polymeric and octahedral.     

Spectral,thermal and biological characterization of complexes with a Schiff base bearing triazole moiety as potential antimicrobial species

Journal of Thermal Analysis and Calorimetry - A novel series of complexes ML(ClO4)·nH2O (M: Co, Ni, Cu, Zn; HL: 2-[(E)-(1H-1,2,4-triazol-3-ylimino)methyl]phenol) have been synthesized and...     

Antioxidative and anti-tumour activities of solid quercetin metal(II) complexes

Six metal(II) complexes with quercetin ML₂ · nH₂O [L = quercetin (3-OH group deprotonated); M = Mn, Co, Ni, Cu, Zn, and Pb; n = 2 or 3] have been prepared and characterized by elemental analysis, complexometric titration, thermal analysis, conductivity, i.r., u.v., ¹H-n.m.r. and fluorescence spectral techniques as well as by cyclic voltammetry. The antioxidative and anti-tumour activities of quercetin · 2H₂O and the complexes were tested by both the MTT and SRB methods. The results show that the suppression ratios of the complexes against the tested tumour cells are superior to quercetin · 2H₂O. The effect of ZnL₂ · 3H₂O reacting with calf thymus DNA was studied by fluorescence methods. The Zn-complex binding to DNA has been determined by fluorescence titration in 0.05 M Tris-HCl, 0.5 M NaCl buffer (pHb = 7.0). The results indicate that the interaction of the complex with DNA is very evident.     

Synthesis,characterization and biological studies of 2-(3,5-dimethylpyrazol-1-yl)benzothiazole complexes of cobalt(II), nickel(II) and copper(II)

Summary Thirteen new complexes, MLX·nH₂O and ML₂(ClO₄)₂· nH₂O [M = Co, Ni, Cu; X = Cl^–, Br^–, NO _f3 ^p– , 1/2SO _f4 ^p2– ; n = 1 or 2; and L = 2-(3,5-dimethylpyrazol-1-yl)benzothiazole], have been synthesized, and characterized by elemental analysis, conductivity measurements, magnetic moments, thermal studies and electronic, i.r. and e.p.r. spectral studies. On the basis of available data probable structures have been proposed. In a few cases the antibacterial and antifungal activities increase on complexation of the ligand with metals.