Jadwiga Skupińska

Nitrobenzene carbonylation in the presence of PdCl2/Fe/I2 and PdCl2Py2/Fe/I2 systems

Abstract The new catalytic system PdCl 2 /Fe/I 2 /Pyridine, active in nitrobenzene carbonylation to ethyl phenylcarbamate (EPC) is presented. For the catalyst composition determined by the following ratio: 0.17/10/1.4/12.4 of its components respectively, at 180°C; under initial CO pressure=4 MPa, after 2 h, a nitrobenzene conversion reached 99.6%, the percentages of the products obtained were: 83.4% EPC and 14% aniline (NB/Pd=540). Influence of initial CO pressure, reaction temperature, reaction time and the catalyst composition on the reaction products, were established.

Reduction of nitrobenzene to aniline with carbon monoxide and water

Modified catalytic system composed of selenium and cocatalysts such as pyridine and aniline, applied in the reduction of nitrobenzene to aniline in the presence of carbon monoxide and water is described. The reaction proceeds at 150–200°C and 3–4 MPa gauge pressure. After 1–2 h the reaction is complete, reaching nitrobenzene conversions of up to 98% with selectivity to aniline near 100%.

ESR investigation of Ti3+ compounds supported on inorganic gels

CpTiCl2-M-surface complexes (M=Al, Si, Mg, Cp=cyclopentadienyl) supported on Al2O3, SiO2, MgO gels are reduced by Et3Al, C3H5MgBr and BuLi to Ti3+ surface compounds which exhibit ESR signals. The g⊥ and g‖ values and asymmetry of these signals depend on the kind of gel and reducing agent.AbstractПоверхностные комплексы CpTiCl2-M (где M=Al, Si, Mg и Cp=циклопентадиенил), нанесенные на гели Al2O3, SiO2 и MgO, были восстановлены с помощью Et3Al, C3H5MgBr, BuLi (Et=−C2H5 и Bu=−C4H9) до поверхностных соединений Ti+3, дающих сигнал ЭПР. Величины g⊥ и g‖ и асиметрия этих сигналов зависят от типа гели и типа восстановителя.

The effect of the components of the PdCl2/Fe/I2/Py catalytic system on nitrobenzene carbonylation to ethyl N-phenylcarbamate

The PdCl2/Fe/I2/Py catalytic system (Py-pyridine), reported to be highly active in the reaction of nitrobenzene carbonylation to ethyl phenylcarbamate was studied. The present paper describes the role of catalyst components and its effect on the activity and selectivity of the catalyst. The increase in the amount of PdCl2 in the system while retaining a constant level of the other catalyst components, results in the increase of both carbamate and aniline yields. The increase in the amount of iron while retaining the other components constant, initially causes an increase in the carbamate yield; however, at Fe: Pd ratios higher than 36, the carbamate yield remains constant. The change in the amount of iron has no effect on the amount of aniline formed in the system. An increase in the amount of iodine in the system while retaining the other components constant, results in a decrease in carbamate yield and a considerable increase in the aniline yield of the reaction products.

Biological activity of Pd(II) complexes with mono- and disubstituted pyridines—Experimental and theoretical studies

Due to the similarity between Pd and Pt, the complexes of palladium(II) can be considered as potential anticancer agents. Activity of six PdCl2(X2Py)2 complexes (Py=pyridine, and X=CH3 or Cl) was measured by MTT test using MCF7, CCRF-SB, PC3 and human B-lymphoblastoid cell lines. We found that the effect of PdCl2(XnPy)2 was cell-specific and time-dependent. Obtained results were discussed and compared with the activation parameters calculated for the hydrolysis of PdCl2(XnPy)2, indicating a correlation between viability of MCF7 and CCRF-SB cells and rates of hydrolysis of the Pd(II) complexes.