Synthesis, Structure, and Radioprotective Activity of the Palladium (II) Complex With Mexidol

New complex compounds of palladium (II) with biologically active ligand 2 - ethyl - 6 methyl - 3 - hydroxy-pyridine - mexidol in acidic medium (pH = 5,3) of the following composition have been synthesized – (C8H12O⊕N)2 [PdCl4]. In this case, the ligand is protonated and as a single-charged cation occupies an external coordination sphere. The structure of the complex is proved by X-ray structure analysis. It is shown that the structure is constructed of an isolated complex anion [PdCl4]2- and cation C8H12O⊕N. The square planar coordination of the palladium atom is formed from three chlorine atoms and the formed tetraacidoanion ligand forms a hydrogen bond. The average length of Pd-Cl bond is 2, 3030 Α°, there are no deviations from 900 valence angles of Cl-Pd-Cl. The palladium atom is not shifted from the plane coordination polyhedron (square) and therefore trance angles of Cl-Pd-Cl are 1800. Two different lengths -2,289 Α° and 2,713 Α° of hydrogen bonds are related to the geometric location of the ligand functional group. The obtained 2 – ethyl – 6 – methyl – 3 -hydroxypyridinetrachloro - palladium - mexidazole was tested for radioprotective properties. Toxicity of the preparation is LD50 - 240 mg/kg of animal weight. Toxicological studies of mexidazole in mice, rats and dogs did not reveal cardiotoxic, immunotoxic, embryonic, nephrotoxic, hematoxic and other types of side effects. Mexidazole is removed from the body with urine 5-8 hours after intravenous injection. The carried out biological test showed that the compound, along with radioprotective properties, has some antitumor activity.

Synthesis, Structure, and Radioprotective Activity of the Palladium (II) Complex with Mexidol

New complex compounds of palladium (II) with biologically active ligand 2 - ethyl - 6 methyl - 3 - hydroxy-pyridine - mexidol in acidic medium (pH = 5,3) of the following composition have been synthesized – . In this case, the ligand is protonated and as a single-charged cation occupies an external coordination sphere. The structure of the complex is proved by X-ray structure analysis. It is shown that the structure is constructed of an isolated complex anion – and cation . The square planar coordination of the palladium atom is formed from three chlorine atoms and the formed tetraacidoanion ligand forms a hydrogen bond. The average length of Pd-Cl bond is 2, 3030 , there are no deviations from 900 valence angles of Cl-Pd-Cl. The palladium atom is not shifted from the plane coordination polyhedron (square) and therefore trance angles of Cl-Pd-Cl are 1800. Two different lengths -2,289 and 2,713 of hydrogen bonds are related to the geometric location of the ligand functional group. The obtained 2 – ethyl – 6 – methyl – 3 -hydroxypyridinetrachloro - palladium - mexidazole was tested for radioprotective properties. Toxicity of the preparation is LD50 - 240 mg/kg of animal weight. Toxicological studies of mexidazole in mice, rats and dogs did not reveal cardiotoxic, immunotoxic, embryonic, nephrotoxic, hematoxic and other types of side effects. Mexidazole is removed from the body with urine 5-8 hours after intravenous injection. The carried out biological test showed that the compound, along with radioprotective properties, has some antitumor activity.

Steric and Electronic Effect of Cp-Substituents on the Structure of the Ruthenocene Based Pincer Palladium Borohydrides

Ruthenocene-based PCPtBu pincer ligands were used to synthesize novel pincer palladium chloride RcF[PCPtBu]PdCl (2a) and two novel palladium tetrahydroborates RcF[PCPtBu]Pd(BH4) (3a) and Rc*[PCPtBu]Pd(BH4) (3b), where RcF[PCPtBu] = κ3-{2,5-(tBu2PCH2)2-C5H2}Ru(CpF) (CpF = C5Me4CF3), and Rc*[PCPtBu] = κ3-{2,5-(tBu2PCH2)2C5H2}Ru(Cp*) (Cp* = C5Me5). These coordination compounds were characterized by X-ray, NMR and FTIR techniques. Analysis of the X-ray data shows that an increase of the steric bulk of non-metalated cyclopentadienyl ring in 3a and 3b relative to non-substituted Rc[PCPtBu]Pd(BH4) analogue (3c; where Rc[PCPtBu] = κ3-{2,5-(tBu2PCH2)2C5H2}Ru(Cp), Cp = C5H5) pushes palladium atom from the middle plane of the metalated Cp ring in the direction opposite to the ruthenium atom. This displacement increases in the order 3c < 3b < 3a following the order of the Cp-ring steric volume increase. The analysis of both X-ray and IR data suggests that BH4 ligand in both palladium tetrahydroborates 3a and 3b has the mixed coordination mode η1,2. The strength of the BH4 bond with palladium atom increases in the order Rc[PCPtBu]Pd(BH4) < Rc*[PCPtBu]Pd(BH4) < RcF[PCPtBu]Pd(BH4) that appears to be affected by both steric and electronic properties of the ruthenocene moiety.

Anagostic Interactions in Alkyl-Fluorenyl-Substituted N‐Heterocyclic Carbene Complexes of Palladium(II)

Two imidazolylidene (Im) complexes of the general formula trans-[PdX2(Im)(pyridine)] (X=Cl (2), Br (3)), in which the N-heterocyclic carbene ligand has one of its nitrogen atoms substituted by a bulky 9-propyl-9-fluorenyl group (PrF), have been prepared and fully characterised by spectroscopic methods and single-crystal X-ray structure analyses. In the solid state, the Im ring plane and the coordination plane of each complex are nearly orthogonal, thereby minimising the steric interactions between the N-substituents and the halide atoms. In both structures two methylenic C–H bonds sit near the dz2 axis point to the palladium atom, resulting in CH⋯Pd separations of 2.58/2.95Å in 2 and 2.74/2.74Å in 3. NMR measurements and DFT calculations indicate that these methylene groups are involved in anagostic CH⋯M interactions but not in significant H⋯X bonding.