N-heterocyclic dithiocarbamate platinum(II) complexes: Unexpected transformation of dithiocarbamate to oxodithiocarbonate in phosphinoplatinum complexes in solution (original) (raw)
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Bi and Trivalent transition metal complexes of dithiocarbamates derived from 2,6- diacetyl pyridine
Some new 3d-series transition metal complexes of types ML{M=Mn(II), Co(II), Ni(II), Cu(II) and Zn(II)} and M’2L3 {M’=Cr(III) and Fe(III)} with dithiocarbamate ligand derived from 2,6-diacetyl pyridine have been prepared by the replacement reaction method. These complexes have been characterized by elemental analysis, conductivity measurements and infrared spectral studies. All the complexes were non-electrolyte in nature. Infrared spectral data of these complexes showed the bidentate behaviour of ligand and the metals were found to be tetra and hexa-coordinated in ML and M’2L3 type of complexes respectively.
RSC Advances, 2016
Heteroleptic platinum(II) dithiocarbamates, of general formula [Pt(DTC)LCl], where DTC = 4-(4-methoxyphenyl)piperazine-1-carbodithioate (1 and 2) and 4-(furan-2-carbonyl)piperazine-1-carbodithioate (3) and L = tri(4-flourophenylphosphine) (1 and 3) and tri(4-chlorophenylphosphine) (2) have been synthesized and characterized by different analytical techniques. These complexes are square planar with picoplatin or phenanthriplatin type steric hindrance from aromatic C–H groups of the phosphine ligand as shown by single-crystal analysis. In 1, the Pt square plane is hindered by two axially oriented hydrogens, whereas by only one in 2 and 3. DNA-binding studies by UV/visible spectroscopy revealed a stronger electrostatic interaction of 1 compared to 2 and 3, and the results are further supported by viscometry and cyclic voltammetric measurements. Their in vitro anticancer activity against five different cancer cell lines using a MTT assay revealed high potency of the complexes. The higher activity of 1 than both 2 and 3 is consistent with DNA binding strength and we speculate that it may be due to the relatively inert nature of platinum towards off-target biomolecules ensured by the hindrance caused by the two axially oriented hydroge
Coordinating ability of methylpiperidine dithiocarbamates towards platinum group metals
Polyhedron, 1985
New rhodium(III), iridium(III), palladium(I1) and platinum(I1) dithiocarbamate complexes of the types M(Rdtc), and M(Rdtc), (Rdtc = 2-, 3-and 4-methylpiperidine dithiocarbamate) have been prepared and characterized by chemidal analyses, conductance measurements, electronic and IR spectral studies, magnetic measurements and thermal analyses (TG and DTG techniques). From the electronic absorption spectra the values of the ligand field parameters were determined; the nephelauxetic parameters are indicative of a strong covalency in the metal-ligand bond. All the complexes here reported are diamagnetic and nonconducting both in the solid state and in DMF solution.
The structural chemistry of zinc(ii) and nickel(ii) dithiocarbamate complexes
Open Chemistry
Dithiocarbamate complexes are of immense interest due to their diverse structural properties and extensive application in various areas. They possess two sulfur atoms that often act as the binding sites for metal coordination in a monodentate, bidentate, or anisodentate fashion. These different coordination modes enhance the possibility for complex formation and make them useful in different areas especially in biomedical fields. A synergy exists in the metal ions and dithiocarbamate moieties, which tends to exert better properties than the respective individual components of the complex. These improved properties have also been attributed to the presence of the C–S bonds. Zinc and nickel ions have been majorly found to bind to the dithiocarbamate in bidentate modes, and consequently different geometries have resulted from this interaction. The aim of this review is to present some studies on the synthesis, structural chemistry, and the relevance of zinc and nickel dithiocarbamates ...
Ditopic dithiocarbamate ligands for the production of trinuclear species
Arabian Journal of Chemistry, 2017
Reactions of group 10 transition metals with the ditopic ligand dipicolyldithiocarbamate (DPDTC) were performed. Thus, 1:2 reactions of [Ni(CH 3 COO) 2 ], [Pd(COD)Cl 2 ] or [Pt(COD)Cl 2 ] with DPDTC produced monomeric complexes of the type [M(j 2-SCS-DPDTC) 2 , M = Ni (1), Pd (2) or Pt (3)] with the dithiocarbamate ligand (DTC) coordinated in a typical chelate j 2-SCS fashion. Interestingly, the reaction of [NiCl 2 ] with DPDTC, under similar conditions, afforded the organic compound 2-(pyridin-2-ylmethyl)imidazo[1,5-a]pyri-dine-3(2 H)-thione (4) as unique product. In order to prove the ditopic nature of the ligand DPDTC, complex [Pd(j 2-SCS-DPDTC) 2 ] (2) was further reacted with [ZnCl 2 ] in a 1:2 M ratio to yield the trinuclear complex [Cl 2 Zn(j 2-NN-DPDTC-SCS-j 2)Pd(j 2-SCS-DPDTC-NN-j 2)ZnCl 2 ] (5). The molecular structures of all compounds were determinate by typical analytical techniques including the unequivocal determination of all structures by single crystal X-ray diffraction analysis. As expected, complexes 1-3 are isostructural, and the metal centres exhibiting slightly distorted square-planar geometries. While in 5, the trinuclear nature of the complex in confirmed exhibiting a nice combination of tetrahedral-square planar-tetrahedral geometries for the Zn-Pd-Zn centres respectively.
The Versatility in the Applications of Dithiocarbamates
International Journal of Molecular Sciences
Dithiocarbamate ligands have the ability to form stable complexes with transition metals, and this chelating ability has been utilized in numerous applications. The complexes have also been used to synthesize other useful compounds. Here, the up-to-date applications of dithiocarbamate ligands and complexes are extensively discussed. Some of these are their use as enzyme inhibitor and treatment of HIV and other diseases. The application as anticancer, antimicrobial, medical imaging and anti-inflammatory agents is examined. Moreover, the application in the industry as vulcanization accelerator, froth flotation collector, antifouling, coatings, lubricant additives and sensors is discussed. The various ways in which they have been employed in synthesis of other compounds are highlighted. Finally, the agricultural uses and remediation of heavy metals via dithiocarbamate compounds are comprehensively discussed.
Journal of Molecular Structure, 2009
Effect of phenyl and benzyl group in heterocyclic dithiocarbamates on the ZnS 4 N chromophore: Synthesis, spectral, valence-bond parameters and single crystal X-ray structural studies on (pyridine)bis(1,2,3,4-tetrahydroquinolinedithiocarbamato)zinc(II) and (pyridine) bis(1,2,3,4-tetrahydroisoquinolinedithiocarbamato)zinc(II) a b s t r a c t Two Zn(II)dithiocarbamates with ZnS 4 N chromophores have been synthesized ([Zn(thqdtc) 2 (py)] (1) and [Zn(thiqdtc) 2 (py)] (2) (where thqdtc = 1,2,3,4-tetrahydroquinolinedithiocarbamate, thiqtc = 1,2,3,4-tetrahydroisoquinolinedithiocarbamate and py = pyridine)) from [Zn(thqdtc) 2 ] (3) and [Zn(thiqdtc) 2 ] (4), respectively. Their structures and properties have been characterized by IR and NMR spectra. The structures of both the complexes were determined by single crystal X-ray crystallography. The observed deshielding of the H-2 protons for 1 and 3 and H-1 and H-3 protons for 2 and 4 in the 1 H NMR spectra is attributed to the drift of electrons from the nitrogen of the NR 2 group, forcing a high electron density towards sulfur via the thioureide p-system. In the 13 C NMR spectra, the most important thioureide (N 13 CS 2 ) carbon signals are observed in the region 204-207 ppm. The upfield shift of NCS 2 carbon signal for 1 (204.2 ppm) from the chemical shift value of 2 (206.9 ppm) is due to electron withdrawing resonance effect of phenyl ring thereby decreasing the double bond character in tetrahydroquinolinedithiocarbamate, whereas benzyl group in tetrahydroisoquinolinedithiocarbamate cannot participate in resonance delocalization in the same way. Single crystal X-ray structural analysis of 1 and 2 showed that the zinc atom is pentacoordinated with four sulfur atoms from the dithiocarbamate ligands and one nitrogen atom from the pyridine. VBS values support the correctness of the determined structure. The lower VBS value of 2 is due to the steric effect exerted by the thiqdtc. The phenyl and benzyl group in the heterocyclic dithiocarbamates influences the electronic properties of 1 and 2. The shift of m C -N (thioureide) and thioureide N 13 CS 2 carbon signals are correlated with the electronic effects of the dithiocarbamate ligands.
2017
Some new first row transition metal complexes of types ML2 {M=Mn(II), Co(II), Ni(II), Cu(II) and Zn(II)} and M'L3 {M'=Cr(III) and Fe(III)} with dithiocarbamate ligand derived from 4-amino-3, 5-bis(pyridine-2-yl)-1,2,4-triazole have been prepared by the replacement reaction. These complexes have been characterized by elemental analysis, conductivity measurements and infrared spectral studies. All the complexes were non-electrolyte in nature. Infrared spectral data of these complexes showed the bidentate behaviour of ligand and metals were found to be tetra and hexa-coordinated in ML2 and M'L3 type of complexes respectively.
Journal of Inorganic Biochemistry, 2004
The precursors [M(ESDTM)Cl 2 ] (M ¼ Pt(II), Pd(II); ESDTM ¼ EtO 2 CCH 2 (CH 3 )NCS 2 Me, S-methyl(ethylsarcosinedithiocarbamate)) were synthesized as previously reported [J. Inorg. Biochem. 83 (2001) 31] and used to obtain [M(ESDT)Cl] n (ESDT ¼ ethylsarcosinedithiocarbamate anion) species. The complexes formed through reaction between [M(ESDT)Cl] n and the two chiral amino-alcohols synephryne (Syn) and norphenylephrine (Nor) have been synthesized, with the ultimate goal of preparing mixed dithiocarbamate/amino metal complexes of the type [M(ESDT)(Am)Cl] (Am ¼ Syn, Nor). These compounds have been isolated, purified and characterized by means of FT-IR, mono-and bidimensional NMR spectroscopy and mass spectrometry ESI/ MS (electronspray mass spectra). The experimental data suggest that in all cases coordination of the dithiocarbamate ligand (ESDT) takes a place through the two sulfur atoms, the -NCSS moiety acting as a symmetrical bidentate chelating group, in a square-planar geometry around the M(II) ion, while the other two coordination positions are occupied by the chlorine atom and the amino-alcohol ligand, respectively. In particular, synephrine and norphenylephrine appear to be bound to the metal atom through the amino nitrogen atom by means of a dative bond.