Russian Journal of Coordination Chemistry

Review of kinetic data on dissociation of the Mn porphyrin complexes in mixed proton-donor solvents depending on the structure of coordination core and porphyrin macrocycle is made. The mechanisms of the processes and the relationship between the stability of complexes, their structures, and composition of mixed solvents containing an acid are considered.

Three palladium(II) complexes of the type [PdCl2(PPh3)L] (L—1-alkylperimidine) have been prepared by reactions of [PdCl2(PPh3)]2 with 1-alkylperimidine. The complexes were characterized by conventional spectroscopic methods and elemental analyses. The incorporation of N-coordinated perimidine complexes of palladium(II) gave high catalytic activity in the Suzuki coupling deactivated aryl chloride substrates.

The mixed salt Cs2[I(OH)3O3] · CsSO4(H)H5IO6 (I) was synthesized for the first time, and its structure and properties were studied by X-ray diffraction, IR and Raman spectroscopies, impedance measurements and DTA method. It crystallizes in trigonal system: a = 7.503(2) Å, c = 16.631(3) Å, space group P3, Z = 2. The crystal structure consists of octahedral IO6 and tetrahedral SO4 fragments, linked by a three-dimensional network of hydrogen bonds, and of the Cs+ ions.

The density functional theory calculations on the manganese complex ([Mn(8-OHQ)3] · CH3OH, 8-OHQ = 8-hydroxyquinoline) is made and its stabilization, molecular orbital composition, orbital energies, and NBO charge distribution have been investigated. The crystal structure of the complex closely resembles the optimized structure. In vitro activities against some antimicrobials (Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa, and Bacillus subtilis) are determined. The antimicrobial activities present a positive correlation between the concentrations and bioactivities of the complex. The relationship between bioactivities and molecular orbitals (HOMO and LUMO orbitals) of the complex is also discussed.

The [Mn(H2O)4]3 · [MnMo9O32] · 2H2O complex was synthesized and studied by X-ray diffraction, thermogravimetry, powder X-ray diffraction, and IR spectroscopy. The crystals are trigonal: space group R32, a = 14.811(2) Å, c = 14.232(2) Å, V = 2703.7(8) Å3, M = 1848.5, Z = 3, ρ(calcd.) = 3.419 g/cm3.

Five compounds of the composition Ln(2,2′-Bipy)(C4H8NCS2)3 · 0.5CH2Cl2 (Ln = Sm (I), Eu (II), Tb (III), Dy (IV), and Tm (V); 2,2′-Bipy = 2,2′-bipyridine) are synthesized. According to the X-ray diffraction data (CIF file CCDC 986259), the crystal structure of compound I consists of molecules of the mononuclear complex [Sm(2,2′-Bipy)(C4H8NCS2)3] and solvate molecules CH2Cl2 (2 : 1). The coordination polyhedron N2S6 of the Sm atom is a distorted tetragonal antiprism. The X-ray diffraction analysis shows that compounds I–V are isostructural. The magnetic properties of compounds I–V are analyzed in the temperature range from 2 to 300 K. At 300 K compounds I and III are photoluminescent in the visible spectral range. The photoluminescence intensity of compound I considerably exceeds that of complex III.

[Pd(NH3)4][Ir0.5Os0.5Cl6] solid solution, isomorphic to [Pd(NH3)4][IrCl6], is synthesized and studied by X-ray powder diffraction and elemental analyses, IR and Raman spectroscopies.