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1.  DNA-Metallodrugs Interactions Signaled by Electrochemical Biosensors: An Overview 
The interaction of drugs with DNA is an important aspect in pharmacology. In recent years, many important technological advances have been made to develop new techniques to monitor biorecognition and biointeraction on solid devices. The interaction between DNA and drugs can cause chemical and conformational modifications and, thus, variation of the electrochemical properties of nucleobases. The propensity of a given compound to interact with DNA is measured as a function of the decrease of guanine oxidation signal on a DNA electrochemical biosensor. Covalent binding at N7 of guanine, electrostatic interactions, and intercalation are the events that this kind of biosensor can detect. In this context, the interaction between a panel of antitumoral Pt-, Ru-, and Ti-based metallodrugs with DNA immobilized on screen-printed electrodes has been studied. The DNA biosensors are used for semiquantitative evaluation of the analogous interaction occurring in the biological environment.
PMCID: PMC2266972  PMID: 18354727
2.  Folding and Unfolding in the Blue Copper Protein Rusticyanin: Role of the Oxidation State 
The unfolding process of the blue copper protein rusticyanin has been studied from the structural and the thermodynamic points of view at two pH values (pH 2.5 and 7.0). When Rc unfolds, copper ion remains bound to the polypeptide chain. Nuclear magnetic resonance data suggest that three of the copper ligands in the folded state are bound to the metal ion in the unfolded form, while the other native ligand is detached. These structural changes are reflected in the redox potentials of the protein in both folded and unfolded forms. The affinities of the copper ion in both redox states have been also determined at the two specified pH values. The results indicate that the presence of two histidine ligands in the folded protein can compensate the change in the net charge that the copper ion receives from their ligands, while, in the unfolded protein, charges of aminoacids are completely transferred to the copper ion, altering decisively the relative stability of its two-redox states.
PMCID: PMC2267886  PMID: 18354738
3.  Complexes of Pd(II) and Pt(II) with 9-Aminoacridine: Reactions with DNA and Study of Their Antiproliferative Activity 
Four new metal complexes {M = Pd(II) or Pt(II)} containing the ligand 9-aminoacridine (9AA) were prepared. The compounds were characterized by FT-IR and 1H, 13C, and 195Pt NMR spectroscopies. Crystal structure of the palladium complex of formulae [Pd(9AA)(μ-Cl)]2 · 2DMF was determined by X-ray diffraction. Two 9-acridine molecules in the imine form bind symmetrically to the metal ions in a bidentate fashion through the imine nitrogen atom and the C(1) atom of the aminoacridine closing a new five-membered ring. By reaction with phosphine or pyridine, the Cl bridges broke and compounds with general formulae [Pd(9AA)Cl(L)] (where L = PPh3 or py) were formed. A mononuclear complex of platinum of formulae [Pt(9AA)Cl(DMSO)] was also obtained by direct reaction of 9-aminoacridine and the complex [PtCl2(DMSO2]. The capacity of the compounds to modify the secondary and tertiary structures of DNA was evaluated by means of circular dichroism and electrophoretic mobility. Both palladium and platinum compounds proved active in the modification of both the secondary and tertiary DNA structures. AFM images showed noticeable modifications of the morphology of the plasmid pBR322 DNA by the compounds probably due to the intercalation of the complexes between base pairs of the DNA molecule. Finally, the palladium complex was tested for antiproliferative activity against three different human tumor cell lines. The results suggest that the palladium complex of formula [Pd(9AA)(μ-Cl)]2 has significant antiproliferative activity, although it is less active than cisplatin.
PMCID: PMC2266976  PMID: 18364995
4.  Interaction of Imidazole Containing Hydroxamic Acids with Fe(III): Hydroxamate Versus Imidazole Coordination of the Ligands 
Solution equilibrium studies on Fe(III) complexes formed with imidazole-4-carbohydroxamic acid (Im-4-Cha), N-Me-imidazole-4-carbohydroxamic acid (N-Me-Im-4-Cha), imidazole-4-acetohydroxamic acid (Im-4-Aha), and histidinehydroxamic acid (Hisha) have been performed by using pH-potentiometry, UV-visible spectrophotometry, EPR, ESI-MS, and H1-NMR methods. All of the obtained results demonstrate that the imidazole moiety is able to play an important role very often in the interaction with Fe(III), even if this metal ion prefers the hydroxamate chelates very much. If the imidazole moiety is in α-position to the hydroxamic one (Im-4-Cha and N-Me-Im-4-Cha) its coordination to the metal ion is indicated unambiguously by our results. Interestingly, parallel formation of (Nimidazole, Ohydroxamate), and (Ohydroxamate, Ohydroxamate) type chelates seems probable with N-Me-Im-4-Cha. The imidazole is in β-position to the hydroxamic moiety in Im-4-Aha and an intermolecular noncovalent (mainly H-bonding) interaction seems to organize the intermediate-protonated molecules in this system. Following the formation of mono- and bishydroxamato mononuclear complexes, only EPR silent species exists in the Fe(III)-Hisha system above pH 4, what suggests the rather significant “assembler activity” of the imidazole (perhaps together with the ammonium moiety).
PMCID: PMC2233813  PMID: 18274616
5.  Characterization of Copper(II) Interactions with Sinefungin, a Nucleoside Antibiotic: Combined Potentiometric, Spectroscopic and DFT Studies 
Interactions between sinefungin and copper(II) ions were investigated. Stoichiometry and stability constants of the metal-free system and two mononuclear complexes present in solution were determined on the basis of potentiometric data analysis. The results were compared to the Cu(II)-ornithine system due to structural similarities between both molecules. Combined spectroscopic and theoretical studies allowed for determination of coordination pattern for the Cu(II)-sinefungin complexes. At acidic pH, copper is bound in “glycine-like” coordination mode, identical with that of ornithine. This involves α-amino group and the carboxyl oxygen. At higher pH, a “bis-complex” is formed by two sinefungin molecules. The second ligand binds in equatorial position displacing two water molecules, what results in the stable {2N,2O} coordination. Both axial positions are supposed to be occupied by N1 nitrogen donors of adenine moiety, what is confirmed by DFT calculations. They interact indirectly with copper(II) through water molecules as the result of dominant syn conformation of purine.
PMCID: PMC2216065  PMID: 18273386
6.  Synthesis, Spectroscopic, and Antimicrobial Studies on Bivalent Nickel and Copper Complexes of Bis(thiosemicrbazone) 
A series of metal complexes of Cu(II) and Ni(II) having the general composition [M(L)X2] with benzil bis(thiosemicarbazone) has been prepared and characterized by element chemical analysis, molar conductance, magnetic susceptibility measurements, and spectral (electronic, IR, EPR, mass) studies. The IR spectral data suggest the involvement of sulphur and azomethane nitrogen in coordination to the central metal ion. On the basis of spectral studies, an octahedral geometry has been assigned for Ni(II) complexes but a tetragonal geometry for Cu(II) complexes. The free ligand and its metal complexes have been tested in vitro against a number of microorganisms in order to assess their antimicrobial properties.
PMCID: PMC2216063  PMID: 18273385
7.  Characterization of Cu(II)-ACC Complexes and Conversion of the Bound ACC into Ethylene in the Presence of Hydrogen Peroxide. Detection of a Brown Intermediate at Low Temperature 
Two copper(II)-ACC complexes were prepared and characterized: [Cu(bpy)(ACC)(H2O)]⋅CO4 (1) and [Cu(ACC)2]3⋅4H2O (2). Their crystallographic structures are described and analyzed. Spectroscopic characterizations (UV-visible and EPR) confirm that the structure is maintained in solution. These complexes are able to produce ethylene in the presence of hydrogen peroxide in an “ACC Oxidase-like” reaction in water and in methanol. The conversion of ACC into ethylene depends on the amount of base, and, in methanol, 3 equivalents of NaOH are needed for optimum activity. The base is proposed to play a role in H2O2 deprotonation. The presence of an exogenic ligand (bpy) is important for the reactivity and may stabilize a reaction intermediate. Indeed, a brown intermediate with an absorption band centered at 433 nm can be detected at low temperature when 1 is treated with 10 equivalents of H2O2.
PMCID: PMC2216062  PMID: 18274607
8.  Transition Metal Complexes of Quinolino[3,2-b]benzodiazepine and Quinolino[3,2-b]benzoxazepine: Synthesis, Characterization, and Antimicrobial Studies 
The synthesis and characterization of title complexes of the ligand Quinolino[3,2-b]benzodiazepine (QBD) and Quinolino[3,2-b]benzoxazepine (QBO) are reported. The complexes have been characterized by elemental analysis, molar conductance, magnetic studies, IR, H1 NMR, and UV-visible studies. They have the stoichiometry [ML2C12], where M=Co(II)/Ni(II), L=QBD/QBO, and [MLC12], where M=Zn(II)/Cd(II), L=QBD/QBO. The antibacterial and antifungal activity of the metal complexes has been investigated. The complexes were found to have higher antimicrobial activity than the parent ligand.
PMCID: PMC2216056  PMID: 18273383
9.  Thermodynamic and Structural Characterization of the Copper(II) Complexes of Peptides Containing Both Histidyl and Aspartyl Residues 
Terminally protected pentapeptides with 2 histidines (Ac-HHVGD-NH2 and Ac-HVGDH-NH2) and the terminally free peptides containing both internal aspartyl and C-terminal histidyl residues (FDAH and VIDAH) have been synthesized, and copper(II) complexes studied by potentiometric, UV-Vis, CD, and EPR spectroscopic techniques in solution. Both thermodynamic and spectroscopic data reveal that side chain donor atoms of aspartyl and histidyl residues have a significant contribution to the metal binding affinity of peptide molecules. In the case of terminally protected peptides, the role of the imidazole-N donor functions is reflected in the enhanced stability of the 3N and 4N coordinated copper(II) complexes. The amino and β-carboxylate groups of FDAH and VIDAH create a very effective metal binding site with the (NH2, N−, β-COO−) and (NH2, N−, N−, β-COO−) coordination modes including the N-termini, while the histidine sites are available for the formation of the (Nim, N−, N−) binding mode resulting in the preference of dinuclear complex formation.
PMCID: PMC2216053  PMID: 18273380
10.  NMR Structure and CD Titration with Metal Cations of Human Prion α2-Helix-Related Peptides 
The 173–195 segment corresponding to the helix 2 of the C-globular prion protein domain could be one of several “spots” of intrinsic conformational flexibility. In fact, it possesses chameleon conformational behaviour and gathers several disease-associated point mutations. We have performed spectroscopic studies on the wild-type fragment 173–195 and on its D178N mutant dissolved in trifluoroethanol to mimic the in vivo system, both in the presence and in the absence of metal cations. NMR data showed that the structure of the D178N mutant is characterized by two short helices separated by a kink, whereas the wild-type peptide is fully helical. Both peptides retained these structural organizations, as monitored by CD, in the presence of metal cations. NMR spectra were however not in favour of the formation of definite ion-peptide complexes. This agrees with previous evidence that other regions of the prion protein are likely the natural target of metal cation binding.
PMCID: PMC2216051  PMID: 18274605
11.  DNA Binding and Photocleavage Studies of Cobalt(III) Polypyridine Complexes: [Co(en)2PIP]3+, [Co(en)2IP]3+, and [Co(en)2phen-dione]3+ 
In this paper, three complexes of type [Co(en)2PIP]3+(PIP=2-phenylimidazo[4,5-f][1,10,] phenanthroline)(1), [Co(en)2IP]3+ (IP = imidazo[4,5-f][1,10,] phenanthroline)(2), and [Co(en)2phen-dione]3+(1,10 phenanthroline 5,6,dione)(3) have been synthesized and characterized by UV/VIS, IR, 1H NMR spectral methods. Absorption spectroscopy, emission spectroscopy, viscosity measurements, and DNA melting techniques have been used for investigating the binding of these two complexes with calf thymus DNA, and photocleavage studies were used for investigating these binding of these complexes with plasmid DNA. The spectroscopic studies together with viscosity measurements and DNA melting studies support that complexes 1 and 2 bind to CT DNA (= calf thymus DNA) by intercalation mode via IP or PIP into the base pairs of DNA, and complex 3 is binding as groove mode. Complex 1 binds more avidly to CT DNA than 2 and 3 which is consistent with the extended planar ring π system of PIP. Noticeably, the two complexes have been found to be efficient photosensitisers for strand scissions in plasmid DNA.
PMCID: PMC1997276  PMID: 18253471
12.  Organosilicon-Containing Thiazole Derivatives as Potential Lipoxygenase Inhibitors and Anti-Inflammatory Agents 
A number of trimethylsiloxyalkyl and trialkylsilylalkyl thiazole derivatives have been evaluated for their anti-inflammatory activity, lipoxygenase inhibiting properties, and cytotoxicity. The investigated compounds have been found to protect in vivo against carrageenin-induced edema, especially 3-(4-trimethylsiloxypiperidin-1-yl)-N-(thiazol-2-yl)-propionamide (21) and 2-amino-3-(γ-trimethylsilylpropyl)thiazolium iodide (22), which exhibited good anti-inflammatory activity: 57.2% CPE inhibition in dose of 0.2 mmol/kg for compound 21 and 55.0% in dose of 0.01 mmol/kg for compound 22. All the compounds tested inhibited soybean lipoxygenase activity. 2-(4-Trimethylsilyloxypiperidin-1-yl)-N-[4-(p-methoxyphenyl)-thiazol-2-yl]-acetamide (19) was the most potent displaying inhibition against lipoxygenase (ID50 = 0.01 mmol). It also possessed moderate cytotoxic effect (LC50 = 13 μ g/mL, 3 × 10−8 mmol/mL) concerning MG-22A cell lines.
PMCID: PMC1950228  PMID: 18256725
13.  Theoretical Investigation of Halogen-Oxygen Bonding and Its Implications in Halogen Chemistry and Reactivity 
Trends in the properties of normal valent and multivalent halogen-oxygen bonding are examined for the isomers of the halogen polyoxide families of the types (YXO2) and (YXO3), Y = Cl, Br, I, H, CH3, X = Cl, Br, I. A qualitative model is formulated on the relationship between the X−O bond distance variations, the ionic character of the bonding, and the degree of halogen valence. The relative stability and enthalpy of formation of each species are also suggested to correlate with the ionic nature of the X−O bonding and the electrostatic character of the Y, YO fragments. In the model presented, halogen hypervalence is interpreted to be the result of partial p → d promotion of lone-pair valence electrons followed by the formation of two, four, or six additional pd hybrid bonds around the halogen atom.
PMCID: PMC1939913  PMID: 17713592
14.  A Mononuclear and a Mixed-Valence Chain Polymer Arising from Copper(II) Halide Chemistry and the Use of 2,2′-Pyridil 
Reactions of 2,2′-pyridil (pyCOCOpy) with CuCl2 · 2H2O and CuBr2 in EtOH yielded the mononuclear complex [Cu(pyCOOEt)2Cl2] · H2O (1) and the one-dimensional, mixed-valence complex [Cu2ICuII(pyCOOEt)2Br4]n (2), respectively. Both complexes crystallize in the triclinic space group P 1¯. The lattice constants are a = 8.382(2), b = 9.778(2), c = 7.814(2), α = 101.17(1), β = 114.55(1), γ = 94.14(1)° for 1 and a = 8.738(1), b = 9.375(2), c = 7.966(1), α = 79.09(1), β = 64.25(1), γ = 81.78(1)° for 2. 2,2′-pyridil undergoes a metal-assisted alcoholysis and oxidation leading to decomposition and yielding the ethyl picolinate (pyCOOEt) ligand. The autoredox process associated with the reduction of copper(II) to copper(I) in the case of complex 2 is discussed in terms of the increased redox activity of the copper(II) bromide system relative to the copper(II) chloride system.
PMCID: PMC1939912  PMID: 18253464
15.  New Perspectives on Thiamine Catalysis: From Enzymic to Biomimetic Catalysis 
This paper is a brief review of the detailed mechanism of action of thiamine enzymes, based on metal complexes of bivalent transition and post-transition metals of model compounds, thiamine derivatives, synthesized and characterized with spectroscopic techniques and X-ray crystal structure determinations. It is proposed that the enzymatic reaction is initiated with a V conformation of thiamine pyrophosphate, imposed by the enzymic environment. Thiamine pyrophosphate is linked with the proteinic substrate through its pyrophosphate oxygens. In the course of the reaction, the formation of the “active aldehyde” intermediate imposes the S conformation to thiamine, while a bivalent metal ion may be linked through the N1' site of the molecule, at this stage. Finally, the immobilization of thiamine and derivatives on silica has a dramatic effect on the decarboxylation of pyruvic acid, reducing the time of its conversion to acetaldehyde from 330 minutes for the homogeneous system to less than 5 minutes in the heterogenous system.
PMCID: PMC1939911  PMID: 17710108
16.  Regioselective Synthesis of Bis(2-halo-3-pyridyl) Dichalcogenides (E = S, Se and Te): Directed Ortho-Lithiation of 2-halopyridines 
A novel method for the preparation of hitherto unknown symmetrical bis(2-halo-3-pyridyl) dichalcogenides (E = S, Se and Te) by the oxidation of intermediate 2-halo-3-pyridyl chalcogenolate, prepared by lithiation of 2-halo pyridines using lithium diisopropylamine is being reported. All the newly synthesized compounds have been characterized through elemental analysis employing various spectroscopic techniques, namely, NMR (1H, 13C, 77Se), infrared, mass spectrometry, and X-ray crystal structures in representative cases.
PMCID: PMC1885866  PMID: 17611613
17.  Lower-Rim Substituted Calixarenes and Their Applications 
This review discusses in detail “calixarenes” since their discovery as by-products of the phenol formaldehyde bakelites till the present scenario wherein calixarene has assumed a new dimension in the field of supramolecular chemistry. Extensive literature exists for calixarenes; but herein we have tried to concentrate on the different lower-rim modified calixarenes with their potential applications. An attempt has also been made to critically evaluate the synthesis procedures for different lower-rim substituted calixarenes.
PMCID: PMC1885865  PMID: 17611612
18.  Chemical Analysis through CL-Detection Assisted by Periodate Oxidation 
The progress of the research work of the author and his colleagues on the field of CL-emission generated by pyrogallol oxidation and further application for the direct determination of periodate and indirect or direct determination of other compounds through flow-injection manifold/CL-detection set up is described. The instrumentation used for these studies was a simple flow-injection manifold that provides good reproducibility, coupled to a red sensitive photomultiplier that gives sensitive CL-detection. In addition, recent reports on studies and analytical methods based on CL-emission generated by periodate oxidation by other authors are included.
PMCID: PMC1878546  PMID: 17611611
19.  Platinum(II) and Palladium(II) Complexes of Pyridine-2-Carbaldehyde Thiosemicarbazone as Alternative Antiherpes Simplex Virus Agents 
The cytotoxicity and the antivirus activity of Pd(II) and Pt(II) complexes with pyridine-2-carbaldehyde thiosemicarbazone (HFoTsc) against HSV replication were evaluated on four HSV strains—two wt strains Victoria (HSV-1) and BJA (HSV-2) and two ACVR mutants with different tk gene mutations R-100 (TKA, HSV-1) and PU (TKN, HSV-2). The experiments were performed on continuous MDBK cells and four HSV 1 and HSV 2 strains were used, two sensitive to acyclovir and two resistant mutants. The five complexes of HFoTsc, [Pt(FoTsc)Cl], [Pt(FoTsc)(H2FoTsc)]Cl2, [Pt(FoTsc)2], [Pd(FoTsc)(H2FoTsc)]Cl2, and [Pd(FoTsc)2], were found to be effective inhibitors of HSV replication. The most promising, active, and selective anti-HSV agent was found to be complex [Pt(FoTsc)(H2FoTsc)]Cl2. This complex could be useful in the treatment of HSV infections, since it is resistant to ACV mutants. PCR study of immediate early 300 bp ReIV Us1 region reveals that the complex [Pt(FoTsc)(H2FoTsc)]Cl2 specifically suppressed wt HSV-1 genome 2 hours after the infection, not inducing apoptosis/necrosis on the 8 hours after virus infection. The target was found to be most probably the viral, instead of the host cell DNA.
PMCID: PMC1876625  PMID: 17541481
20.  Co(III) and Ni(II) Complexes Containing Bioactive Ligands: Synthesis, DNA Binding, and Photocleavage Studies 
DNA binding and photocleavage characteristics of a series of mixed ligand complexes of the type [M(bpy)2qbdp](PF6)n·xH2O (where M = Co(III) or Ni(II), bpy = 2.2′-bipryidine, qbdp = Quinolino[3,2-b]benzodiazepine, n = 3 or 2 and x = 5 or 2) have been investigated. The DNA binding property of the complexes with calf thymus DNA has been investigated by using absorption spectra, viscosity measurements, as well as thermal denaturation studies. Intrinsic binding constant (Kb) has been estimated under similar set of experimental conditions. Absorption spectral studies indicate that the Co(III) and Ni(II) complexes intercalate between the base pairs of the CT-DNA tightly with intrinsic DNA binding constant of 1.3 × 106 and 3.1 × 105 M−1 in Tris-HCl buffer containing 50 mM NaCl, respectively. The proposed DNA binding mode supports the large enhancement in the relative viscosity of DNA on binding to quinolo[3,2-b]benzodiazepine. The oxidative as well as photo-induced cleavage reactions were monitered by gel electrophoresis for both complexes. The photocleavage experiments showed that the cobalt(III) complex can cleave pUC19 DNA effectively in the absence of external additives as an effective inorganic nuclease.
PMCID: PMC1876624  PMID: 17541480
21.  Spectroscopic, Thermal and Biological Studies on Some Trivalent Ruthenium and Rhodium NS Chelating Thiosemicarbazone Complexes 
The synthetic, spectroscopic, and biological studies of sixteen ring-substituted 4-phenylthiosemicarbazones and 4-nitrophenyl-thiosemicarbazones of anisaldehyde, 4-chlorobenzaldehyde, 4-fluorobenzaldehyde, and vanillin with ruthenium(III) and rhodium(III) chlorides are reported here. Their structures were determined on the basis of the elemental analyses, spectroscopic data (IR, electronic, 1H and 13C NMR) along with magnetic susceptibility measurements, molar conductivity and thermogravimetric analyses. Electrical conductance measurement revealed a 1 : 3 electrolytic nature of the complexes. The resulting colored products are monomeric in nature. On the basis of the above studies, three ligands were suggested to be coordinated to each metal atom by thione sulphur and azomethine nitrogen to form low-spin octahedral complexes with ruthenium(III) while forming diamagnetic complexes with rhodium(III). Both ligands and their complexes have been screened for their bactericidal activities and the results indicate that they exhibit a significant activity.
PMCID: PMC1852900  PMID: 17505530
22.  Synthesis and Properties of N-Bromosuccinimide Derivatives of Ammonium Dialkyl/Alkylene Dithiophosphates 
Reaction of N-bromosuccinimide with ammonium salt of alkylene (dialkyl) dithiophosphates, [OGOPS2NH4; G=−CMe2CMe2−CH2CMe2CH2−, CMe2CH2CHMe2−, CH2CH2CHMe2−; (RO)2PS2NH4; R=C2H5, n−C3H7, i−C3H7], in 1 : 1 molor ratio in refluxing benzene solution yields red/brown-colored sticky liquids. These newly synthesized complexes have been characterised by physicochemical and spectroscopic techniques (MW, IR, NMR [1H and 31P]). The computational semiempirical calculations (MOPAC6P/c) have also been studied for these complexes. On the basis of the above studies, the formation of P−S−N chemical linkage has been established.
PMCID: PMC1852899  PMID: 17492049
23.  The Nature of the Chemical Bond in Linear Three-Body Systems: From I3− to Mixed Chalcogen/Halogen and Trichalcogen Moieties 
The 3 centre-4 electrons (3c-4e) and the donor/acceptor or charge-transfer models for the description of the chemical bond in linear three-body systems, such as I3− and related electron-rich (22 shell electrons) systems, are comparatively discussed on the grounds of structural data from a search of the Cambridge Structural Database (CSD). Both models account for a total bond order of 1 in these systems, and while the former fits better symmetric systems, the latter describes better strongly asymmetric situations. The 3c-4e MO scheme shows that any linear system formed by three aligned closed-shell species (24 shell electrons overall) has reason to exist provided that two electrons are removed from it to afford a 22 shell electrons three-body system: all combinations of three closed-shell halides and/or chalcogenides are considered here. A survey of the literature shows that most of these three-body systems exist. With some exceptions, their structural features vary continuously from the symmetric situation showing two equal bonds to very asymmetric situations in which one bond approaches to the value corresponding to a single bond and the second one to the sum of the van der Waals radii of the involved atoms. This indicates that the potential energy surface of these three-body systems is fairly flat, and that the chemical surrounding of the chalcogen/halogen atoms can play an important role in freezing different structural situations; this is well documented for the I3− anion. The existence of correlations between the two bond distances and more importantly the linearity observed for all these systems, independently on the degree of their asymmetry, support the state of hypervalency of the central atom.
PMCID: PMC2276819  PMID: 18389065
24.  Synthesis, Spectroscopic, and Antimicrobial Studies of Binuclear Metallocene (M = Ti, Zr, or Hf) Derivatives of Bis(mercaptoazoles) 
The reactions of (η5 − C5H5)2MCl2 (M = Ti, Zr, or Hf) with mercaptoazoles (LH2), namely, bis(mercaptotriazoles), bis(mercap- tooxadiazoles), and bis(mercaptothiadiazoles) in 2 : 1 molar ratio, respectively, have been studied in dry tetrahydrofuran in the presence of n-butylamine and the binuclear complexes of the type [{(η − C5H5)2 M}2(L)] (M = Ti/Zr/Hf) are obtained. Tentative structural conclusions are drawn for the reaction products based upon elemental analysis, electrical conductance, magnetic moment, and spectral data (UV-Vis, IR, 1H NMR, and 13C NMR). FAB-mass spectra of few complexes of each series were also carried out to confirm the binuclear structures. Studies were conducted to assess the growth-inhibiting potential of the complexes synthesized, and the ligands against various fungal and bacterial strains.
PMCID: PMC2275056  PMID: 18368146

Results 1-24 (24)