Platinum (II) and palladium (II) complexes: synthesis, antimicrobial and antifungal activity

The study aims to synthesize and examine the biological activity of mono- and binuclear platinum (II) and palladium (II) complexes containing terminal and bridging nitrite ligands against the test cultures of Bacillus subtilis B4647, Aspergillus brasiliensis (niger) F679, Pseudomonas aeruginosa B8243, and Escherichia coli. Through the interaction of mononuclear platinum (II) and palladium (II) complexes, dimeric complexes having nitrite ligands were synthesized. The composition and structure of these complexes were established using elemental analysis, conductometry, potentiometry, cryoscopy, infrared spectroscopy, X-ray diffraction analysis, and X-ray fluorescence analysis. A way to coordinate nitrite ligands with the central atom was established. Antimicrobial and antifungal properties were evaluated according to the capability of the synthesized complexes to inhibit the activity of bacteria and fungi via diffusion in agar and in vitro dilution. The minimum inhibitory and bactericidal concentrations of the complexes suppressing the visible growth of microorganisms and fungi, as well as exhibiting their bactericidal effect, ranged from 62.5–125 μmol/dm3. The obtained results revealed a high activity of the palladium (II) binuclear complex of the non-electrolytic type and the platinum (II) binuclear complex of the cationic type. Unlike mononuclear complexes, palladium and platinum binuclear complexes demonstrate higher antibacterial activity. Antibacterial effectiveness exhibited by the palladium complex of the non-electrolytic type against bacteria Bacillus subtilis and Escherichia coli, as well as fungi Aspergillus niger, is more pronounced. The only exception is the antimicrobial activity of the palladium complex against Pseudomonas aeruginosa, which is comparable to that of the binuclear platinum complex of the cationic type. By changing the structure of the complex, the composition and charge of the inner sphere, the number of coordination centers, as well as the nature and denticity of ligands, it is possible to achieve a higher toxic effect of the complexes against bacteria and fungi.

Synthesis and Characterization of New Guanine Complexes of Pt(IV) and Pd(II) by X-Ray Diffraction and Hirshfeld Surface Analysis

The aim of the work was to synthesize new perspective compounds of palladium and platinum with nitrogenous bases (guanine), promising for use in biomedicine and catalysis. The article describes the synthesis of new [PdCl2(HGua)2]Cl2·H2O and [PtCl5(HGua)]·2H2O compounds using wet chemistry methods. The structure of the obtained single crystals was established by the method of single crystal X-ray diffraction. The complexes have an M-N bond, and the organic ligand is included in the first coordination sphere. The analysis of Hirshfeld surfaces for the obtained complexes and their analogues for the analysis of intermolecular interactions was carried out. In the palladium complex we obtained, π-halogen and π-stacking interactions were found; in analogues, such interactions were not found. π-halogen and halogen interactions were found in structure of platinum complex and its analogues.

The catalytic mechanism of the Suzuki-Miyaura reaction

Experimental and theoretical 13C kinetic isotope effects are utilized to obtain atomistic insight into the catalytic mechanism of the Pd(PPh3)4 catalyzed Suzuki-Miyaura reaction of aryl halides and aryl boronic acids. Under catalytic conditions, we establish that oxidative addition of aryl bromides occurs to a 12-electron monoligated palladium complex (Pd(PPh3)). For aryl iodides, the first irreversible step in the catalytic cycle precedes oxidative addition and is shown to be binding of the iodoarene to Pd(PPh3). Our results suggest that the commonly proposed oxidative addition to the 14-electron Pd(PPh3)2 complex can occur only in the presence of excess added ligand or under stoichiometric conditions. The transmetalation step, under catalytic conditions, is shown to proceed via a tetracoordinate boronate (8B4) intermediate with a Pd-O-B linkage.