The complexes PdII(qcq)(OAc) and PtII(qcq)Cl have been synthesized using environmentally benign synthesized ligands and characterized by elemental analyses: Fourier transform infrared spectroscopy, UV–visible spectroscopy, 1H NMR spectroscopy, and X‐ray diffraction. The catalytic activity of the complex was assessed, in different media, for the Mizoroki–Heck coupling reaction for typical aryl halides and terminal olefins under aerobic conditions. Since the base and the solvent were found to influence the efficiency of the reaction, reaction conditions, temperature, time, and the amount of K3PO4 and a mixture of H2O/PEG, were optimized. We found, for the Mizoroki–Heck reaction coupling less reactive aryl chloride derivatives with olefins, promising activity for palladium catalysts. The electrochemical behavior of Hqcq and the Pd(II) complex was investigated by cyclic voltammetry and irreversible PdII/I reductions were observed. Hqcq and the Pd(II) and Pt(II) complexes were also screened for their in vitro antibacterial activity. They showed promising antibacterial activity comparable to that of the antibiotic penicillin.
Homoleptic dinuclear complexes [M2(qpyzc)2] (M=Cu (1) or Ni (2) were obtained from the readily synthesised trischelate pyrazole‐based qpyzc ligand (H2qpyzc=8‐quinoline‐1H‐pyrazole‐3‐carboxamide). Their crystal and molecular structures, magnetic properties, and UV‐vis spectra were reported alongside with DFT and TD‐DFT calculations. Trigonality index τ’4 values of 0.25 and 0.21 for the Cu and Ni centres, respectively reveal a marked distortion from square planar geometry. The two metal coordination planes within a complex are tilted towards each other with 40.2(1)° for Cu(II) and 34.5(2)° for Ni(II). The central six‐membered M2N4 metallocycle is almost planar and the two anionic pyrazolate rings are tilted towards each other by 37.4(1)° (1) and 38.5(2)° (2), respectively. Regardless of this peculiar bonding situation magnetic measurements on 1 are in line with medium‐sized antiferromagnetic coupling with a coupling constant of J=−100 cm−1, an isotropic g value of 2.11 and an S=0 ground state. Complex 2 seems to be diamagnetic. DFT calculations gave an excellent agreement between calculated and experimental metrics of the complexes and supported the prevalence of the singlet ground state for 1. TD‐DFT calculated UV‐vis absorption spectra agree well with observed absorptions and the red colour of both compounds.
A potentiometric thiocyanate-selective sensor based on copper(II) bis(benzoylacetone)propylenediimine complex as a new neutral carrier for a thiocyanate-selective electrode is reported. The response mechanism is discussed in view of the UV spectroscopy technique. The sensor displays a near Nernestian slope of -57.4 ± 0.5 mV per decade. The working concentration range of the electrode is 8.0×10 -7 -1.0×10 -1 M with a detection limit of 7.4×10 -7 M. The response time of the sensor in the all concentration ranges is very short (5-10 s). The response of the sensor is independent of pH, in the pH range of 1.7-11.5. The best performance was obtained with a membrane composition of 32.69% PVC, 57.34% dibutyl phthalate, 6.82% complex and 3.15% methyltrioctylammonium chloride (MTOAC) as additive. The proposed electrode is more selective than other proposed methods for determination of thiocyanate ion over a wide variety of common inorganic and organic anions and it was successfully applied to direct determination of thiocyanate in the presence of other anions in biological, water and waste water samples.
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