New Pd(II) and Pt(II) complexes with N,S-chelated pyrazolonate ligands: molecular and supramolecular structure and preliminary study of their in vitro antitumoral activity.

New Pd(II) and Pt(II) complexes [ML2] (HL=a substituted 2,5-dihydro-5-oxo-1H-pyrazolone-1-carbothioamide) have been synthesized by reacting K2MCl4 (M=Pd, Pt) or Pd(OAc)2 with beta-ketoester thiosemicarbazones. The structures of seven of these complexes were determined by X-ray diffraction. Although all exhibit a distorted square-planar coordination with trans- or (in one case) cis-[MN2S2] kernels, their supramolecular arrangements vary widely from isolated molecules to 3D-networks.

Electrospray ionization mass spectrometry in the structural characterization of some diphenyllead(IV) thiosemicarbazonates.

The behavior in electrospray ionization mass spectrometry (ESI-MS) conditions of some complexes formed by Pb(C6H5)2(OAc)2 with salicylaldehyde, 2-ketobutyric acid, pyridine-2-carbaldehyde, 2-acetylpyridine, and 2-benzoylpyridine thiosemicarbazones, was studied in detail with the aid of collisional experiments performed by ion trap. The homoleptic complexes of tridentate thiosemicarbazonate dianions (TSC2-) lose the phenyl groups first, destabilizing the high oxidation state of the metal and leading to Pb(II) complexes in which the TSC2- ligand or a part of it remains coordinated to the metal. The main difference among the complexes derives from the presence of a carboxylate group on the 2-ketobutyric acid thiosemicarbazonato ligand, which probably interacts with a Na+ cation leading to ESI-generated [M+Na]+ species.

Reactions of thiosemicarbazones derived from beta-keto amides and beta-keto esters with Zn(II) and Cd(II) acetates: influence of metal, substitution, reagent ratio and temperature on metal-induced cyclization.

Zinc(II) and cadmium(II) acetates were reacted in methanol under various experimental conditions with thiosemicarbazones derived from beta-keto amides or beta-keto esters (HTSC). Some of these reactions afforded thiosemicarbazonate complexes [M(TSC)2] with IR and NMR spectra compatible with N,S-coordination, but most gave complexes [ML2], where HL is a substituted 2,5-dihydro-5-oxo-1H-pyrazole-1-carbothioamide resulting from cyclization of the HTSC. Some of these pyrazolonates and two of the HL ligands were studied by X-ray diffractometry, and their structures are discussed.

Compositional and structural variety of diphenyllead(IV) complexes obtained by reaction of diphenyllead dichloride with thiosemicarbazones.

The reactions of PbPh(2)Cl(2) in methanol with acetophenone, salicylaldehyde, pyridine-2-carbaldehyde, 2-acetylpyridine, and 2-benzoylpyridine thiosemicarbazones (HATSC, HSTSC, HPyTSC, HAcPyTSC, and HBPyTSC, respectively) were explored. Despite the similarities among these ligands, the reactions afforded solids with very diverse compositions and structural characteristics, which were in most cases analyzed by X-ray diffractometry (as was the structure of the free ligand HBPyTSC). In the complexes [PbPh(2)Cl(2)(HATSC)](2), [PbPh(2)Cl(2)(HSTSC)(2)], [(PbPh(2)Cl(HPyTSC)(2))][PbPh(2)Cl(3)(MeOH)](2), and [PbPh(2)Cl(PyTSC)] the metal atoms are surrounded by more or less distorted octahedral coordination polyhedra; if both strong and weak interactions are considered, the lead atom in [PbPh(2)Cl(AcPyTSC)] has coordination number 7 and distorted pentagonal bipyramidal coordination geometry, while [(PbPh(2)(BPyTSC))(2)(PbPh(2)Cl(4))].

Metal-induced cyclization of thiosemicarbazones derived from beta-keto amides and beta-keto esters: open-chain and cyclized ligands in zinc(II) complexes.

The reactions of Zn(OAc)(2) with acetoacetanilide, methyl acetoacetate, o-acetoacetanisidide, and ethyl 2-methylacetoacetate thiosemicarbazones (HTSC(1), HTSC(2), HTSC(3), and HTSC(4), respectively) were explored in methanol. With HTSC(1), HTSC(2), and HTSC(3), following isolation of the corresponding zinc(II) thiosemicarbazonates [Zn(TSC(x))(2)] (x = 1, 2, 3), the mother liquors afforded pyrazolonate complexes [ZnL(1)(2)(H(2)O)] (HL(1) = 2,5-dihydro-3-methyl-5-oxo-1H-pyrazole-1-carbothioamide) that had been formed by cyclization of the corresponding TSC(-). The reaction of HTSC(4) with zinc(II) acetate gave only the pyrazolonate complex [ZnL(2)(2)(H(2)O)] (HL(2) = 2,5-dihydro-3,4-dimethyl-5-oxo-1H-pyrazole-1-carbothioamide).

Dichlorobis(3,5-dimethylpyrazole-N2)methylphenyltin(IV).

The title compound, [SnCl(2)(CH(3))(C(6)H(5))(C(5)H(8)N(2))(2)], was obtained by reaction of dichloromethylphenyltin(IV) and 3, 5-dimethylpyrazole (dmpz) in chloroform, and was recrystallized from acetone. The structure consists of octahedral all-trans [SnMePhCl(2)(dmpz)(2)] molecules, with the Sn atom coordinated to two C [Sn-C 2.127 (5) and 2.

Synthesis, structure, and spectroscopic properties of acetato(dimethyl)(pyridine-2-carbaldehydethiosemicarbazonato)tin(IV) acetic acid solvate, [SnMe2(PyTSC)(OAc)].HOAc. Comparison of its biological activity with that of some structurally related diorganotin(IV) bis(thiosemicarbazonates).

The synthesis, X-ray structure, behavior in solution, and biological properties of the complex [SnMe2(PyTSC)(OAc)].HOAc (HPyTSC = pyridine-2-carbaldehydethiosemicarbazone) are reported. The tin atom of this complex is coordinated to an N,N,S-tridentate PyTSC- anion, to a monodentate acetate ion, and to the two methyl groups in an approximately pentagonal bipyramidal environment with a vacant equatorial position.