1079097-20-3Relevant academic research and scientific papers
Synthesis, crystal structures, magnetic properties and photoconductivity of C60 and C70 complexes with metal dialkyldithiocarbamates M(R2dtc)x, where M = CuII, CuI, AgI, ZnII, CdII, HgII, Mn II, NiII, and PtII; R = Me, Et, and nPr
Konarev, Dmitri V.,Kovalevsky, Andrey Y.,Khasanov, Salavat S.,Saito, Gunzi,Lopatin, Dmitri V.,Umrikhin, Alexey V.,Otsuka, Akihiro,Lyubovskaya, Rimma N.
, p. 1881 - 1895 (2006)
New complexes of fullerenes C60 and C70 with metal dialkyldithiocarbamates, [M(R2dtc)x]·[C 60(70)]·[Solvent], R = Et [M = CuII (C60, 1; C70, 2), CuI (C60, 3; C70, 4), AgI (C60, 5), ZnII (C 60, 6), CdII (C60, 7; C70, 8), HgII (C60, 9), MnII (C70, 10)], R = Et and Me [M = CuII (C60, 11), and ZnII (C 60, 12)], and R = nPr [M = CuII (C60, 13), NiII (C60, 14), and PtII (C60, 15)] were obtained. M(R2dtc)x efficiently cocrystallized with fullerene molecules as tetrahedral monomers (6, 12), dimers (1, 7, 11), and tetramers (3, 4). Fullerene molecules form closely packed hexagonal and square layers in 1, 7, and 11, hexagonal and tetragonal 3D structures in 6 and 12, and island motifs in 3 and 4. Complexes 1-15 have a neutral ground state. However, the formation of the complexes with fullerenes changes the environment of paramagnetic CuII and MnII. The EPR spectra of 1, 2, 11, and 13 are essentially modified relative to those of pristine Cu(R 2dtc)2 because of a weak coordination of CuII to fullerene and a flattening of the central (NCS2)2Cu fragments. Complex 10 shows a spectrum exhibiting features from 50 to 600 mT and manifests strong antiferromagnetic coupling of spins with a Weiss temperature of -96 K and the maximum of magnetic susceptibility at 46 K. Such magnetic behavior can be explained by the formation of [Mn(Et2dtc) 2]2 dimers in 10. The illumination of the crystals of 1, 2, and 7 by white light results in up to a 103 increase in photocurrent. The photoconductivity spectra have maxima at 470, 450-650, and 660 nm for 1, 2, and 7, respectively. Photogeneration of free charge carriers is realized by photoexcitation of Cu(Et2dtc)2 in 1 and 2, and by charge transfer from Cd(Et2dtc)2 to C60 molecules in 7. The decrease of photocurrent in 1 and 7 in a weak magnetic field with B0 0.5 T was found. Wiley-VCH Verlag GmbH & Co. KGaA, 2006.
A single-source approach to metastable Ni3S4 crystallites and their optical properties
Chen, Xiangying,Wang, Zhenghua,Wang, Xiong,Wan, Junxi,Liu, Jianwei,Qian, Yitai
, p. 1294 - 1295 (2004)
Metastable Ni3S4 with good crystallinity has been firstly synthesized via a single-source approach using nickel diethyldithiocarbamate as precursor under hydrothermal conditions. The optical properties of the as-prepared Ni3S4 are evaluated. It is found that the reaction temperature is of importance to the formation of Ni 3S4 crystallites.
Anagostic interactions, revisiting the crystal structure of nickel dithiocarbamate complex and its antibacterial and antifungal studies
Husain, Ahmad,Nami, Shahab A.A.,Singh, Suneel P.,Oves,Siddiqi
, p. 33 - 40 (2011)
The synthesis of Ni(dtc)2 [dtc = diethyldithiocarbamate] has been achieved by the interaction of NiL(ClO4)2 with sodium diethyldithiocarbamate. Although single crystal structure of this complex was already reported (R = 10.6%), we were able to refine crystal structure up to R = 2.99%. We also observed rare C-H?Ni anagostic interactions generally exhibited by d8 complexes which were overlooked previously. To investigate the structure of Ni(dtc)2 in solution, variable temperature NMR spectra in solution have also been recorded between 25 and -50 °C. Ni(dtc)2 was also tested for antibacterial and antifungal activities. It showed higher activity against the bacteria and fungi than the known antibiotics.
Spectroelectrochemical studies of nickel(I) complexes: One-electron reduction of nickel(II) complexes of dithiocarbamate and phosphine ligands [Ni(R2NCS2)x(Ph2PCH 2CH2PPh2)2-x]2-x (x = 0, 1, 2)
Bowmaker, Graham A.,Boyd, Peter D. W.,Campbell, Graeme K.,Hope, Janet M.,Martin, Raymond L.
, p. 1152 - 1159 (1982)
The electrochemical generation and stability of nickel(I) complexes of the type [Ni(R2NCS2)x(dpe)2-x]1-x (x = 0, 1, 2; dpe = Ph2PCH2CH2PPh2) have been investigated with use of the methods of electron spin resonance (ESR) spectroscopy and cyclic voltammetry. Reduction of the bis(dithiocarbamato) complexes NiII(R2NCS2)2 at a Pt electrode in dichloromethane solution yields an initial planar nickel(I) species, which interconverts to a new nickel(I) species with reversed g values. In contrast Ni(dpe)22+ undergoes two closely spaced reductions, the first of which corresponds to a nickel(I) complex with four equivalent phosphorus ligands bound to the metal. The mixed-ligand complex [NiII(R2NCS2)(dpe)]PF6 may be reduced to a nickel(I) species with two equivalent phosphorus ligands bound to the metal. This species undergoes a series of further reactions, resulting in an overall disproportionation to NiII(R2NCS2)2 and Ni0(dpe)2. The kinetics and mechanism of this reaction have been investigated with use of ESR spectra and cyclic voltammetry. The nickel(I) complexes [Ni(R2NCS2)2]- can also be generated by γ irradiation of frozen solutions of Ni(R2NCS2)2, and these have been characterized with use of ESR spectroscopy.
Induction of Necroptosis in Cancer Stem Cells using a Nickel(II)-Dithiocarbamate Phenanthroline Complex
Flamme, Marie,Cressey, Paul B.,Lu, Chunxin,Bruno, Peter M.,Eskandari, Arvin,Hemann, Michael T.,Hogarth, Graeme,Suntharalingam, Kogularamanan
, p. 9674 - 9682 (2017)
The cytotoxic properties of a series of nickel(II)-dithiocarbamate phenanthroline complexes is reported. The complexes 1–6 kill bulk cancer cells and cancer stem cells (CSCs) with micromolar potency. Two of the complexes, 2 and 6, kill twice as many breast cancer stem cell (CSC)-enriched HMLER-shEcad cells as compared to breast CSC-depleted HMLER cells. Complex 2 inhibits mammosphere formation to a similar extent as salinomycin (a CSC-specific toxin). Detailed mechanistic studies suggest that 2 induces CSC death by necroptosis, a programmed form of necrosis. Specifically, 2 triggers MLKL phosphorylation, oligomerization, and translocation to the cell membrane. Additionally, 2 induces necrosome-mediated propidium iodide (PI) uptake and mitochondrial membrane depolarisation, as well as morphological changes consistent with necroptotosis. Strikingly, 2 does not evoke necroptosis by intracellular reactive oxygen species (ROS) production or poly(ADP) ribose polymerase (PARP-1) activation.
Cytotoxicity, anti-microbial studies of M(II)-dithiocarbamate complexes, and molecular docking study against SARS COV2 RNA-dependent RNA polymerase
Al-Janabi, Ahmed S. M.,Saleh, Abdulrahman M.,Hatshan, Mohammad R.
, p. 1104 - 1115 (2021)
Ten transition metal dithiocarbamate (DTC)complexes of the type [M(κ2-Et2DT)2] (1–5), and [M(κ2-PyDT)2] (6–10) (where M?=?Co, Ni, Cu, Pd, and Pt; Et2DT?=?diethyl dithiocarbamate; PyDT?=?pyrrolidine dithiocarbamate) were synthesized and characterized by different methods. The dithiocarbamate acted as bidentate chelating ligands to afford a tetrahedral complexes with Co(II) ion and square planner with other transition metal ions. The dithiocarbamate complexes showed good activity against the pathogen bacteria species. The results showed the Pt-dithiocarbamate complexes are more active against all the tested bacteria than the Pd-dithiocarbamate complex. The dithiocarbamate complexes displayed the maximum inhibition zone against E. coli bacteria, whereas the lowest activity of the dithiocarbamate against Salmonella typhimurium bacteria. The cytotoxicity of the Pd(II) and Pt(II) complexes was screened against the MCF-7 breast cancer cell line and the complexes showed moderate activity compared with the cis-platin. The results indicated that the MCF7 cells treated with 500?μgml of ligands and Pd(II) and Pt(II) complexes after 24 hr exposure showed intercellular space and dead cells. Finally, molecular docking studies were carried out to examine the binding mode of the synthesized compounds against the proposed target; SARS COV2 RNA-dependent RNA polymerase.
Influence of Pyridine on the Multielectron Redox Cycle of Nickel Diethyldithiocarbamate
Richburg, Chase S.,Farnum, Byron H.
, (2019/11/14)
Two-electron (2e-)-transfer reactions for monometallic complexes of first-row transition metals are uncommon because of the tendency of these metals to proceed through sequential one-electron (1e-)-transfer pathways. For this chemistry to be observed, structural changes upon electron transfer are often needed to shift the 1e- redox potentials to a condition of potential inversion where 2e- transfer becomes favorable. Nickel(II) dithiocarbamate complexes take advantage of these conditions to drive 2e- oxidation from NiII to NiIV. Here, we have studied the electrochemistry of NiII(dtc)2, where dtc- is N,N-diethyldithiocarbamate in an acetonitrile solvent as a function of the scan rate and added pyridine to gain further insight into the mechanism for its 2e- oxidation to [NiIV(dtc)3]+. The scan rate dependence revealed evidence for an ECE mechanism in which the chemical step constituted ligand exchange between [NiIII(dtc)2]+ and NiII(dtc)2. A pseudo-first-order rate constant for this reaction of 34 s-1 was obtained at 1 mM NiII(dtc)2. The addition of pyridine to the electrolyte solution showed pronounced changes to the cyclic voltammetry (CV) that were consistent with the formation of a pyridine-bound NiIII complex, [NiIII(dtc)2(py)2]+, which was stable at high scan rates but decomposed to [NiIV(dtc)3]+ at low scan rates. The observed decomposition rate constant was well modeled with two parallel decay pathways, one through the dipyridine [NiIII(dtc)2(py)2]+ and another through a monopyridine [NiIII(dtc)2py]+. Overall, these data point to a mechanism for oxidation from NiII(dtc)2 to [NiIV(dtc)3]+ that proceeds through an undercoordinated [NiIII(dtc)2]+ complex, which can be trapped on the time scale of CV experiments using pyridine ligands. These studies provide insight into how we may be able to control 1e- versus 2e- redox chemistry using the coordination environment and nickel oxidation state.
Synthesis and reactivity of some mixed ligand complexes of Ni(II) involving dithiocarbamates and hard bases
Rajendiran,Ramalingam,Thiruneelakandan
, p. 1101 - 1103 (2007/10/03)
A few mixed ligand complexes of the general formula, [Ni(L)(DMG)] [where L=(H5C2)2NCS2- (dedtc-), (HOH4C2)NHCS2- (meadtc-), (HOH4C2)2NCS2- (deadtc-), H10C5NCS2- (pipdtc-), oxine(OX); DMG= dimethylglyoxime] have been synthesised and characterized by elemental analysis, IR, electronic spectra and thermogravimetric analysis.
A 1,10-phenanthroline adduct complex of bis(N,N-diethyldithiocarbamato)nickel(II)
Emmenegger
, p. 2210 - 2214 (2008/10/08)
The first example of the addition of a chelating diamine to square-planar bis(dithiocarbamato)nickel(II), forming an octahedral complex, is reported. The equilibrium constant of the reaction bis(N,N-diethyldithiocarbamato)nickel(II) (abbreviated Ni(dtc)2) + o-phenanthroline (abbreviated phen) = Ni(dtc)2·phen has been determined spectrophotometrically from 293 to 313 K in toluene, acetone, and chloroform to get the enthalpy and entropy of the reaction in these three solvents. The higher stability in toluene (K298 = 2237 M-1) as compared to that in chloroform (K298 = 96 M-1) is mainly due to a more negative enthalpy of reaction in toluene (-49.7 kJ mol-1 in toluene vs -40.1 kJ mol-1 in chloroform), while the higher stability in acetone (K298 = 1126 M-1) as compared to that in chloroform is mainly due to a less negative entropy of reaction (-64.5 J K-1 mol-1 in acetone vs -96.2 J K-1 mol-1 in chloroform). By two independent thermodynamic cycles ΔH, ΔS, and ΔG of the above reaction in the solid state have been evaluated. The main difference between the solution and the solid-state reaction is the much less negative entropy of the latter. The rate of formation of Ni(dtc)2·phen has been investigated by stopped flow. It is second order, and the rate constants are proportional to the stability constants of the complex in the respective solvent. The rate of decomposition is first order and shows no solvent dependence. The energy of the desolvation of the reactants in the course of forming the reaction intermediate has been correlated to the activation energy of the formation of Ni(dtc)2·phen.
THE DIRECT ELECTROCHEMICAL SYNTHESIS OF DIALKYLDITHIOCARBAMATE AND DIETHYLDITHIOPHOSPHATE COMPLEXES OF MAIN GROUP AND TRANSITION METALS
Geloso, Corrado,Kumar, Rajesh,Lopez-Grado, Jaime Romero,Tuck, Dennis G.
, p. 928 - 932 (2007/10/02)
Dialkyldithiocarbamate derivatives (R2NCS2)nM of a number of metals (M=Fe, Co, Ni, Cu, Ag, Zn, Cd, In, Tl) have been synthesised in good yield by electrochemical oxidation of appropriate sacrificial anodes in non-aqueous solutions of either the corresponding tetraalkylthiuran disulphide (R2NCS2)2 (R=Me, Et) or a mixture of carbon disulphide plus the secondary amine R2NH (R=Et, i-Pr; R2NH=piperidine).Similar experiments with solutions of (EtO)2P(S)SH (=HL) gave MLn* derivatives (M=Fe, Co, Ni, Cu, Ag, Au, Zn, Cd, Hg, Ga, In, Tl) while in the presence of HL+1,10-phenanthroline, MLn.phen derivatives were obtained for M=V, Mn, Fe, Co, Zn, and Ga.
