Transition metal complexes derived from ketone based N(4)-substituted thiosemicarbazones: Crystal structures and spectral studies

Thiosemicarbazones have recently attracted considerable attention due to their ability to form tridentate chelates with transition metal ions through either two nitrogen and sulfur atoms, N–N–S or oxygen, nitrogen and sulfur atoms, O–N–S. Considerable interest in thiosemicarbazones and their transition metal complexes has also grown in the areas of biology and chemistry due to biological activities such as antitumoral, fungicidal, bactericidal, antiviral and nonlinear optical properties. They have been used for metal analyses, for device applications related to telecommunications, optical computing, storage and information processing.The versatile applications of metal complexes of thiosemicarbazones in various fields prompted us to synthesize the tridentate NNS-donor thiosemicarbazones and their metal complexes. As a part of our studies on transition metal complexes with these ligands, the researcher undertook the current work with the following objectives. 1. To synthesize and physico-chemically characterize the following thiosemicarbazone ligands: a. Di-2-pyridyl ketone-N(4)-methyl thiosemicarbazone (HDpyMeTsc) b. Di-2-pyridyl ketone-N(4)-ethyl thiosemicarbazone (HDpyETsc) 2. To synthesize oxovanadium(IV), manganese(II), nickel(II), copper(II), zinc(II) and cadmium(II) complexes using the synthesized thiosemicarbazones as principal ligands and some anionic coligands. 3. To study the coordination modes of the ligands in metal complexes by using different physicochemical methods like partial elemental analysis, thermogravimetry and by different spectroscopic techniques. 4. To establish the structure of compounds by single crystal XRD studies

Complexes of cytotoxic chelators from the dipyridyl ketone isonicotinoyl hydrazone (HPKIH) analogues

In an effort to better understand the antiproliferative effects of the tridentate hydrazone chelators di-2-pyridyl ketone isonicotinoyl hydrazone (HPKIH) and di-2-pyridyl ketone benzoyl hydrazone (HPKBH), we report the coordination chemistry of these ligands with the divalent metal ions, Mn, Co, Ni, Cu, and Zn. These complexes are compared with their Fe-II analogues which were reported previously. The crystal structures of Co(PKIH)(2), Ni(PKIH)(2), Cu(PKIH)(2), Mn(PKBH)(2), Ni(PKBH)(2), Cu(PKBH)(2), and Zn(PKBH)(2) are reported where similar bis-tridenate coordination modes of the ligands are defined. In pure DMF, all complexes except the Zn-II compounds exhibit metal-centered M-III/II (Mn, Fe, Co, Ni) or M-II/I (Cu) redox processes. All complexes show ligand-centered reductions at low potential. Electrochemistry in a mixed water/DMF solvent only elicited metal-centered responses from the Co and Fe complexes. Remarkably, all complexes show antiproliferative activity against the SK-N-MC neuroepithelioma cell line similar to (HPKIH) or significantly greater than that of the (HPKBH) ligand which suggests a mechanism that does not only involve the redox activity of these complexes. In fact, we suggest that the complexes act as lipophilic transport shuttles that allow entrance to the cell and enable the delivery of both the ligand and metal which act in concert to inhibit proliferation.

Formation of an unusual copper(II) complex from the degradation of a novel tricopper(II) carbohydrazone complex

An unusual copper(II) complex [Cu(L-1a)(2)Cl-2] CH3OH center dot H2O center dot H3O+Cl- (1a) was isolated from a solution of a novel tricopper(II) complex [Cu-3(HL1)Cl-2]Cl-3 center dot 2H(2)O (1) in methanol. where L-1a is 3-(2-pyridyl)triazolo [1,5-a]-pyridine, and characterized with single crystal X-ray diffraction study. The tricopper(II) complex of potential ligand 1,5-bis(di-2-pyridyl ketone) carbohydrazone (H2L1) was synthesized and physicochemically characterized, while the formation of the complex la was followed by time-dependant monitoring of the UV-visible spectra. which reveals degradation of ligand backbone as intensity loss of bands corresponding to O -> Cu(II) charge transfer.

Spectral studies and crystal structures of some transition metal complexes of N4-substituted semicarbazones

The present work is concentrated on the studies of two novel semicarbazones, di-2-pyridyl ketone-N4-phenyl-3-semicarbazone (HL1) and quinoline-2-carboxaldehyde-N4-phenyl-3-semicarbazone (HL2). The compositions of these semicarbazones were determined by the CHN analyses. For the characterization of these compounds we have used IR, UV and NMR spectral studies. The molecular structure of quinoline-2-carboxaldehyde-N4-phenyl-3- semicarbazone (HL2) was obtained by single crystal X-ray diffraction studies. Also, we have synthesized Zn(II), Cd(II), Cu(II), Ni(II), Co(II) and Mn(II) complexes of these semicarbazones, HL1 and HL2. These complexes were characterized by various spectroscopic techniques, magnetic and conductivity studies. We could isolate single crystals of some Zn(II) and Cd(II) compounds suitable for X-ray diffraction studies. For other complexes we could not isolate single crystals of good quality for single crystal X-ray diffraction studies.

Formation of an unusual copper(II) complex from the degradation of a novel tricopper(II) carbohydrazone complex

An unusual copper(II) complex [Cu(L1a)2Cl2] CH3OH H2O H3O+Cl (1a) was isolated from a solution of a novel tricopper(II) complex [Cu3(HL1)Cl2]Cl3 2H2O (1) in methanol, where L1a is 3-(2-pyridyl)triazolo [1,5-a]-pyridine, and characterized with single crystal X-ray diffraction study. The tricopper(II) complex of potential ligand 1,5-bis(di-2-pyridyl ketone) carbohydrazone (H2L1) was synthesized and physicochemically characterized, while the formation of the complex 1a was followed by time-dependant monitoring of the UV–visible spectra, which reveals degradation of ligand backbone as intensity loss of bands corresponding to O?Cu(II) charge transfer

Chemistry of molecular and supramolecular structures of vanadium(IV) and dioxygen-bridged V(V) complexes incorporating tridentate hydrazone ligands

Four hydrazone ligands: 2-benzoylpyridine benzoyl hydrazone (HBPB), di-2-pyridyl ketone nicotinoyl hydrazone (HDKN), quinoline-2-carbaldehyde benzoyl hydrazone (HQCB), and quinoline-2-carbaldehyde nicotinoyl hydrazone (HQCN) and four of their complexes with vanadyl salts have been synthesized and characterized. Single crystals of HBPB and complexes [VO(BPB)(l2-O)]2 (1) and [VO(DKN)(l2-O)]2 ½H2O (2) were isolated and characterized by X-ray crystallography. Each of the complexes exhibits a binuclear structure where two vanadium(V) atoms are bridged by two oxygen atoms to form distorted octahedral structures within cis-N2O4 donor sets. In most complexes, the uninegative anions function as tridentate ligands, coordinating through the pyridyl- and azomethine-nitrogen atoms and enolic oxygen whereas in complex [VO(HQCN)(SO4)]SO4 4H2O (4) the ligand is coordinated in the keto form. Complexes [VO(QCB)( OMe)] 1.5H2O (3) and 4 are found to be EPR active and showed well-resolved axial anisotropy with two sets of eight line pattern

Vanadium complexes with hydrazone or thiosemicarbazone ligands as potential anti-mycobacterium tuberculosis agents

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

An environmentally friendly analytical procedure for nickel determination by atomic and molecular spectrometry after cloud point extraction in different samples

Cloud point extraction (CPE) was employed for separation and preconcentration prior to the determination of nickel by graphite furnace atomic absorption spectrometry (GFAAS), flame atomic absorption spectrometry (FAAS) or UV-Vis spectrophotometry. Di-2-pyridyl ketone salicyloylhydrazone (DPKSH) was used for the first time as a complexing agent in CPE. The nickel complex was extracted from the aqueous phase using the Triton X-114 surfactant. Under optimized conditions, limits of detection obtained with GFAAS, FAAS and UV-Vis spectrophotometry were 0.14, 0.76 and 1.5 mu g L-1, respectively. The extraction was quantitative and the enrichment factor was estimated to be 27. The method was applied to natural waters, hemodialysis concentrates, urine and honey samples. Accuracy was evaluated by analysis of the NIST 1643e Water standard reference material.

Dipyridyl thiosemicarbazone chelators with potent and selective antitumor activity form iron complexes with redox activity

There has been much interest in the development of iron (Fe) chelators for the treatment of cancer. We developed a series of di-2-pyridyl ketone thiosemicarbazone (HDpT) ligands which show marked and selective antitumor activity in vitro and in vivo. In this study, we assessed chemical and biological properties of these ligands and their Fe complexes in order to understand their marked activity. This included examination of their solution chemistry, electrochemistry, ability to mediate redox reactions, and antiproliferative activity against tumor cells. The higher antiproliferative efficacy of the HDpT series of chelators relative to the related di-2-pyridyl ketone isonicotinoyl hydrazone (HPKIH) analogues can be ascribed, in part, to the redox potentials of their Fe complexes which lead to the generation of reactive oxygen species. The most effective HDpT ligands as antiproliferative agents possess considerable lipophilicity and were shown to be charge neutral at physiological pH, allowing access to intracellular Fe pools.

Solution processable poly(2,5-dialkyl-2,5-dihydro-3,6-di-2-thienyl- pyrrolo[3,4-c]pyrrole-1,4-dione) for ambipolar organic thin film transistors

Solution processable diketopyrrolopyrrole (DPP)-bithiophene polymers (PDBT) with long branched alkyl side chains on the DPP unit are synthesized. These polymers have favourable highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels for the injection and transport of both holes and electrons. Organic thin film transistors (OTFTs) using these polymers as semiconductors and gold as source/drain electrodes show typical ambipolar characteristics with very well balanced high hole and electron mobilities (μ h = 0.024 cm 2 V -1 s -1 and μ e = 0.056 cm 2 V -1 s -1). These simple and high-performing polymers are promising materials for ambipolar organic thin film transistors for low-cost CMOS-like logic circuits.

Synthesis and Spectroscopic Investigations of Complexes of Lanthanide Nitrates with N-(4-Hethyl-2-Pyridyl)-Acetamide

New complexes of Lanthanide nitrates with N-(4-methyl-2-pyridyl)-acetamide (4-me-aapH) of the general formulae. [Ln(4-me-aapH)2] [NO3] (where Ln=La=La-Yb and Y)have been synthesized and haracterised by chemical analysis, molar conductivity and physical methods such as infrared, 13C NMR an electronic spectra in the visible region. Molar conductance and infrared data point to the presence to the coordinated nitrates groups. Infrared and 13C NMR data have been interpreted in terms of the coordination of the legand to the metal ion through the oxygen of the secondary amide and nitrogen of the hetrocyclic ring, in a bidentate fashion. Coordination number of ten seems probable for the complexes.

Vibrational and 1H NMR spectra of N-(2-pyridyl)-thioformamide and N-(2-pyridyl)thioacetamide

The Raman and infrared spectra of N-(2-pyridyl) thioformamide and N-(2-pyridyl)-thioacetamide have been measured. The assignment of the bands is aided by the complete normal coordinate treatment for all the vibrations of N-(2-pyridyl)thioformamide and its N-deuterated molecule using a Urey—Bradley force function for the in-plane vibrations and a valence force function for the out of plane vibrations. Variable temperature 1H NMR study of the two pyridylthionamides has also been performed. It is inferred that while N-(2-pyridyl)thioformamide favours a cis —CSNH— group, the other compound favours a trans —CSNH— grouping at ambient temperature.

Some metal complexes with n-(2-pyridyl)thioacetamide and n-(2-pyridyl)thiobenzamide

The Cu(II). Zn(II) and Cd(II) chloride and bromide complexes of N-2(2-pyridyl)thioacetamide and N-(2-pyridyl)thiobenzamide have been prepared. The infrared and 1H and 13C NMR spectra of the complexes and the free ligands have been analysed to determine the coordination sites. It was concluded that N-(2-pyridyl)thioacetamide behaves as a bidentate ligand, chelating to the metal via pyridine nitrogen and thionamide sulfur atoms while the other ligand, N-(2-pyridyl)thiobenzamide coordinates to the metal atom as a unidentate through the pyridine nitrogen atom. Conformations of the free ligands are discussed.