Structural and spectral investigations on some new Ni(II) complexes of di-2-pyridyl ketone N(4)-phenylthiosemicarbazone

Ni(II)complexes(1-5)ofdi2pyridylketoneN(4)-phenylthiosemicarbazone (HL) have been synthesized and spectrochemically characterized. Elemental analyses revealed a NiL2 center dot 2H(2)O stoichiometry for compound 1. However, the single crystals isolated revealed a composition NiL, - 0.5(H,0)0.5(DMF). The compound crystallizes into a monoclinic lattice with the space group P-21/n. Complexes 2. 3 and 4 are observed to show a 1:1:1 ratio of metal: thioseicarbazone:gegenion, with the general formula NiLX center dot yH(2)O [X = NCS. Y = 2 for 2; X = Cl, Y = 3 for 3 and X = N-3, y = 4.5 for 4]. Compound 5 is a dimer with a metal:thiosemicarbazone:gegenion ratio of 2:2: 1. with the formula [Ni,L,(SO4)1 - 4H(2)O (c) 2007 Elsevier Ltd. All rights reserved.

Structural and spectral investigations on some new Ni(II) complexes of di-2-pyridyl ketone N(4)-phenylthiosemicarbazone

Ni(II) complexes (1-5) of di-2-pyridyl ketone N(4)-phenylthiosemicarbazone (HL) have been synthesized and spectrochemically characterized. Elemental analyses revealed a NiL2 center dot 2H(2)O stoichiometry for compound 1. However, the single crystals isolated revealed a composition NiL, - 0.5(H,0)0.5(DMF). The compound crystallizes into a monoclinic lattice with the space group P-21/n. Complexes 2. 3 and 4 are observed to show a 1:1:1 ratio of metal: thioseicarbazone:gegenion, with the general formula NiLX center dot yH(2)O [X = NCS. Y = 2 for 2; X = Cl, Y = 3 for 3 and X = N-3, y = 4.5 for 4]. Compound 5 is a dimer with a metal:thiosemicarbazone:gegenion ratio of 2:2: 1. with the formula [Ni,L,(SO4)1 - 4H(2)O (c) 2007 Elsevier Ltd. All rights reserved.

The syntheses, characterizations, X-ray crystal structures and properties of Cu(I) complexes of a bis-bidentate schiff base ligand

Bis-bidentate Schiff base ligand L and its two mononuclear complexes [CuL(CH3CN)(2)]ClO4 (1)and [CuL(PPh3)(2)]ClO4 (2)have been prepared and thoroughly characterized by elemental analyses, IR, UV-Vis, NMR spectroscopy and X-ray diffraction analysis. In both the complexes the metal ion auxiliaries adopt tetrahedral coordination environment. Their reactivity, electrochemical and photophysical behavior have been studied. Complex 1 shows reversible Cu-II/I couple with potential 0.74 V versus Ag/AgCl in CH2Cl2. At room temperature L is weakly fluorescent in CH2Cl2, however in Cu(I)complexes 1 and 2 the emission in quenched. (C) 2009 Elsevier B. V. All rights reserved.

Structure determination and biochemical studies on Bacillus stearothermophilus E53Q serine hydroxymethyltransferase and its complexes provide insights on function and enzyme memory

Serine hydroxymethyltransferase (SHMT) belongs to the alpha-family of pyridoxal 5'-phosphate-dependent enzymes and catalyzes the reversible conversion of L-Ser and etrahydrofolate to Gly and 5,10-methylene tetrahydrofolate. 5,10-Methylene tetrahydrofolate serves as a source of one-carbon fragment in many biological processes. SHMT also catalyzes the tetrahydrofolate-independent conversion of L-allo-Thr to Gly and acetaldehyde. The crystal structure of Bacillus stearothermophilus SHMT (bsSHMT) suggested that E53 interacts with the substrate, L-Ser and etrahydrofolate. To elucidate the role of E53, it was mutated to Q and structural and biochemical studies were carried out with the mutant enzyme. The internal aldimine structure of E53QbsSHMT was similar to that of the except for significant changes at Q53, Y60 and Y61. The wild-type enzyme, carboxyl of Gly and side chain of L-Ser were in two conformations in the respective external aldimine structures. The mutant enzyme was completely inactive for tetrahydrofolate-depen dent cleavage of L-Ser, whereas there was a 1.5-fold increase in the rate of tetrahydrofolate-independent reaction with L-allo-Thr. The results obtained from these studies suggest that E53 plays an essential role in tetrahydrofolate/5-formyl tetrahydrofolate binding and in the proper positioning of C beta of L-Ser for direct attack by N5 of tetrahydrofolate. Most interestingly, the structure of the complex obtained by cocrystallization of E53QbsSHMT with Gly and 5-formyl tetrahydrofolate revealed the gem-diamine form of pyridoxal 5'-phosphate bound to Gly and active site Lys. However, density for 5-formyl tetrahydrofolate was not observed. Gly carboxylate was in a single conformation, whereas pyridoxal 5'-phosphate had two distinct conformations. The differences between the structures of this complex and Gly external aldimine suggest that the changes induced by initial binding of 5-formyl tetrahydrofolate are retained even though 5-formyl tetrahydrofolate is absent in the final structure. Spectral studies carried out with this mutant enzyme also suggest that 5-formyl tetrahydrofolate binds to the E53QbsSHMT-Gly complex forming a quinonoid intermediate and falls off within 4 h of dialysis, leaving behind the mutant enzyme in the gemdiamine form. This is the first report to provide direct evidence for enzyme memory based on the crystal structure of enzyme complexes.

Family of Mixed-Valence Oxovanadium(IV/V) Dinuclear Entities Incorporating N4O3-Coordinating Heptadentate Ligands: Synthesis, Structure, and EPR Spectra

Dinuclear ((VVV)-V-IV) oxophenoxovanadates of general formula [V2O3L] have been synthesized in excellent yields by reacting bis(acetylacetonato)oxovanadium(IV) with H3L in a 2:1 ratio in acetone under an N-2 atmosphere. Here L3- is the deprotonated form of 2,6-bis[{{(2-hydroxybenzyl)(N',N'-(dimethylamino)ethyl)}amino}methyl]-4-methylphenol (H3L1), 2,6-bis[{{(5-methyl-2-hydroxybenzyl)(N',N'-(dimethylamino)ethyl)}amino}methyl]-4-methylphenol (H3L2) 2,6-bis[ {{(5-tert-butyl-2-hydroxybenzyl)(N',N'-(dimethylamino)ethyl)}amino}methyl]-4-methylphenoI (H3L3), 2,6-bis[{{(5-chloro-2-hydroxybenzyl)(N',N'-(dimethylamino)ethyl)}amino}methyl]-4-methylphenol (H3L4) , 2,6-bis[{{(5-bromo-2-hydroxybenzyl)(N',N'-(dimethylamino)ethyl)}amino}methyl]-4-methylphenol (H3L5), or 2,6-bis[{{(5-methoxy-2-hydroxybenzyl)(N',N'-(dimethylamino)ethyl)}amino}methyl]-4-methylphenol (H3L6). In [V2O3L1], both the metal atoms have distorted octahedral geometry. The relative disposition of two terminal V=O groups in the complex is essentially cis. The O=V...V=O torsion angle is 24.6(2)degrees. The V-O-oxo-V and V-O-phenoxo-V angles are 117.5(4) and 93.4(3)degrees, respectively. The V...V bond distance is 3.173(5) Angstrom. X-ray crystallography, IR, UV-vis, and H-1 and V-51 NMR measurements show that the mixed-valence complexes contain two indistinguishable vanadium atoms (type 111). The thermal ellipsoids of O2, O4, C10, C14, and C15 also suggests a type III complex in the solid state. EPR spectra of solid complexes at 77 K display a single line indicating the localization of the odd electron (3d(xy)(1)). Valence localization at 77 K is also consistent with the V-51 hyperfine structure of the axial EPR spectra (3d(xy)(1) ground state) of the complexes in frozen (77 K) dichloromethane solution: S = 1/2, g(parallel to) similar to 1.94, g(perpendicular to) similar to 1.98, A(parallel to) similar to 166 x 10(-4) cm(-1), and A(perpendicular to) similar to 68 x 10(-4) cm(-1). In contrast isotropic room-temperature solution spectra of the family have 15 hyperfine lines (g(iso) similar to 1.974 and A(iso) similar to 50 x 10(-4) cm(-1)) revealing that the unpaired electron is delocalized between the metal centers. Crystal data for the [V2O3L1].CH2Cl2 complex are as follows: chemical formula, C32H43O6N4C12V2; crystal system, monoclinic; space group, C2/c; a = 18.461(4), b = 17.230(3), c = 13.700(3) Angstrom; beta = 117.88(3)degrees; Z = 8.

Antipyrine complexes of rare-earth nitrates

Antipyrine complexes of eight rare-earth nitrates of the composition M(C11H12N2O)3 (NO3)3 where M = La, Ce, Pr, Nd, Sm, Gd, Er, and Y, have been prepared by a new, simple method and characterised. The complexes undergo exothermic decomposition at ~3oo°C. Infrared and U.V. spectral studies of the complexes indicate that antipyrine coordinates to metal through oxygen. The nature of the nitrate bonding is discussed in the light of infrared evidence, and conductivity studies in nitromethane and dimethylformamide.

Oxalato complexes of oxovanadium (IV)

Oxalato oxovanadium (IV) complexes with neutral ligand molecules like dimethyl sulphoxide (DMSO) and antipyrine (Apy), VOOX·2DMSO and VOOX·2Apy and complex oxalates of oxovanadium (IV)-(NH4)2[VOOX2]·2H2O, (NH4)2[(VO)2OX3]·6H2O and (NH4)2[(VO)2OX3] have been prepared and characterized by different methods. In the divanadyl complexes, V-V and V-O-V-O types of bonding are shown to be absent by magnetic and spectral data and a bridged oxalato group co-ordinated to the two vanadium atoms is shown to be present, in addition to the usual bidentate oxalate groups. The possible stereochemical arrangements are indicated for the complexes.

Antipyrine complexes of titanium(IV), zirconium(iv), thorium(IV) and uranium(VI) perchlorates

Antipyrine complexes of TiO2+, ZrO2+, Zr4+, Th4+ and UO2+2 perchlorates with molecular formulae TiO(Apy)4(ClO4)2, ZrO(Apy)3(ClO4)2, Zr(Apy)6(ClO4)4, Th(Apy)7(ClO4)4 and UO2(Apy)5(ClO4)2 have been prepared and characterized. The complexes are stable in air at room temperature and decompose exothermally at ~3OO °C. The i.r. study indicates the bonding of the antipyrine to the metal ion through its carbonyl oxygen. The nature of the bonding of the perchlorate and the stereochemistry of the complexes are discussed in the light of infrared spectra, conductivity in solvents of different polarity, and molecular weight measurements. From the UO2+2 group frequencies, the force constant K and rU-o are found to be 6.29 × 105 dynes/ cm-1 and 1.74 Å, respectively.

Dimethyl sulphoxide complexes of titanyl, zirconyl and thorium perchlorates

TiO·5DMSO(ClO4)2, ZrO·8DMSO(ClO4)2 and Th·12DMSO(ClO4)4 are prepared by reaction of the respective metal perchlorates with an excess of dimethyl sulphoxide. The last two complexes yield ZrO·6DMSO(ClO4)2 and Th·6DMSO(ClO4)4 on heating around 185°C, while the titanyl complex explodes at 190°C. The extra DMSO molecules in the zirconyl and thorium complexes seem to be held in the lattice. In the parent complexes, the co-ordinated DMSO molecules are bonded by oxygen to the metal atoms while in the DMSO complexes of zirconyl and thorium perchlorates, obtained by heating at 185°C, the bonding involves the sulphur, indicating a change in the bonding during the process of heating.

Some sulphoxide complexes of iron

Diphenyl sulphoxide(DPSO) and dimethyl sulphoxide(DMSO) complexes of iron(II) having the composition [Fe(DPSO)6](ClO4)2, Fe(DPSO)2Cl2, Fe(DPSO)3Br2, Fe(DPSO)4I2, [Fe (DMSO)3Cl2]. DMSO and [Fe(DMSO)3Br2]. DMSO and DPSO complexes of iron(III), Fe(DPSO)2 Cl3 have been prepared and their physico-chemical properties studied. Their magnetic moments at room temperature show them to be spin-free complexes. The i.r. spectra reveal that oxygen is the donor atom in all the complexes. The electronic spectra of iron(II) complexes indicate octahedral coordination for the metal ion. A salt like structure [Fe(DPSO)4Cl2][FeCl4], is suggested for the iron (III) complex, where the cationic species has distorted octahedral structure while the anionic species has tetrahedral structure.

Photocytotoxicity and DNA cleavage activity of L-arg and L-lys Schiff base oxovanadium(IV) complexes having phenanthroline bases

Oxovanadium(IV) complexes [VO(sal-argH)(B)] Cl (1-3) and [VO(sal-lysH)(B)] Cl (4-6), where sal-argH2 and sal-lysH(2) are N-salicylidene-L-arginine and N-salicylidene-L-lysine Schiff bases and B is a phenanthroline base, viz. 1,10-phenanthroline (phen in 1 and 4); dipyrido[3,2-d: 2', 3'-f] quinoxaline (dpq in 2 and 5) and dipyrido[3,2-a: 2', 3'-c] phenazine (dppz in 3 and 6), have been prepared, characterized and their DNA photocleavage activity studied. Complex 1, characterized by X-ray crystallography, shows the presence of a vanadyl group in VIVO3N3 coordination geometry with a tridentate Schiff base having a pendant guanidinium moiety and bidentate phen ligand. The complexes exhibit a d-d band at similar to 715 nm in 20% DMF-Tris-HCl buffer. The complexes are redox active showing cathodic and anodic responses near -1.0 V and 0.85 V (vs. SCE) for the V(IV)-V(III) and V(V)-V(IV) couples, respectively, in DMF-Tris-HCl buffer. The complexes bind to calf thymus DNA giving Kb values in the range of 3.8 x 10(4) to 1.6 x 10(5) M-1. Thermal denaturation and viscosity data suggest DNA groove binding nature of the complexes. The complexes do not show any `chemical nuclease'' activity in dark in the presence of 3-mercaptopropionic acid or H2O2. The dpq and dppz complexes are efficient photocleavers of plasmid DNA in UV-A (365 nm) and red light (676 nm) via singlet oxygen pathway. The dppz complexes exhibit photocytotoxicity in HeLa cancer cells giving IC50 values of 15.4 mu M for 3 and 17.5 mu M for 6 in visible light while being non-toxic in dark giving IC50 values of > 100 mu M.

Crystal structure of 2-thiophene-2-yl-3(thiophene-2-carboxylideneamino)-1,2-dihydroquinazolin-4(3H)-one and the synthesis, spectral and thermal studies of its transition metal(II) complexes

The synthesis of manganese(II), cobalt(II), nickel(II), copper(II), zinc(II) and cadmium(II) complexes of a new ligand 2-thiophene-2-yl-3(thiophene-2-carboxylidene-amino)-1,2-dihydroquinazolin-4(3H)-one (TTCADQ) is described. The ligand and metal complexes were characterized by elemental analysis, conductivity measurements, spectral (u.v.-vis., i.r., 1D n.m.r., 2D hetcor and e.p.r.) and thermal studies. The formation of 1,2-dihydroquinazolin-4(3H)-one rather than hydrazone, in the reaction of aromatic aldehyde and o-aminobenzoylhydrazide is proved by single crystal X-ray diffraction and 2D hetcor n.m.r. studies. On the basis of elemental analysis, u.v.-vis.spectroscopy and magnetic moment studies, six coordinate geometry for all the complexes was proposed. The i.r. spectral studies reveal the bidentate behaviour of the ligand.

Ferrocene-Promoted Photoactivated DNA Cleavage and Anticancer Activity of Terpyridyl Copper(II) Phenanthroline Complexes

Ferrocene-appended copper(II) complexes [Cu( Fc-tpy)(B)](ClO4)(2) (1-3) and [Cu(Ph-tpy)(dppz)](ClO4)(2) (4) as control, where Fc-tpy is 4'-ferroceny1-2,2':6',2 ''-terpyridine, Ph-tpy is 4'-pheny1-2,2':6',2 ''-terpyridine, and B is a phenanthroline base, viz., 1,10-phenanthroline (phen, 1), dipyridoquinoxaline (dpq, 2), and dipyridophenazine (dppz, 3), were prepared and structurally characterized, and their DNA binding, photoactivated DNA cleavage activity, and cytotoxic properties were studied [Fe = (eta(5)-C5H4)Fe-11(eta(5)-C5H5)]. Complexes 1 and 3 as hexafluorophosphate salts were structurally characterized by X-ray crystallography. Molecular structures of [Cu(Fc-tpy)(phen)](PF6)(2) (1a) and [Cu(Fc-tpy)(dppz)](PF6)(2)center dot MeCN (3a center dot MeCN) show a distorted square-pyramidal geometry at copper(II), with the Fc-tpy ligand and the phenanthroline base showing respective tridentate and bidentate binding modes. The phenanthroline base exhibits axial-equatorial bonding, while the Fc-tpy ligand binds at the basal plane. The complexes showed quasi-reversible cyclic voltammetric responses near 0.45 and -0.3 V vs SCE in aqueous DMF-0.1 M KCl assignable to the Fc(+)-Fc and Cu(II) Cu(1) redox couples, respectively. The complexes bind to DNA, giving K-b values of 1.4 x 10(4) to 5.6 x 10(5) M-1 in the order 4 similar to 3 > 2 > 1. Thermal denaturation and viscometric titration data suggest groove and/or partial intercalative mode of DNA binding of the complexes. The complexes showed chemical nuclease activity in the presence of 3-mercaptopropionic acid (0.5 mM) or H2O2 (0.25 mM). Complexes 2-4 showed plasmid DNA cleavage activity in visible light, forming (OH)-O-center dot radicals. The Fc-tpy complex 3 showed better DNA photocleavage activity than its Ph-tpy analogue. The ferrocene moiety in the dppz complex 3 makes it more photocytotoxic than the Ph-tpy analogue 4 in HeLa cells.