Побожій С.І. Мистецтвознавчі нариси: монографія. - Суми, 2013. - 416 с.: 112 арк. іл.

Рецензія Сергія Дегтярьова на книжку "Побожій С.І. Мистецтвознавчі нариси: монографія. - Суми, 2013. - 416 с.: 112 арк. іл.".Рецензия Сергея Дегтярёва на книгу "Побожій С.І. Мистецтвознавчі нариси: монографія. - Суми, 2013. - 416 с.: 112 арк. іл.".Review of the book "Побожій С.І. Мистецтвознавчі нариси: монографія. - Суми, 2013. - 416 с.: 112 арк. іл." by Sergiy Degtyaryov

Iron(II) Complexes of the Linear <i>rac-</i>Tetraphos‑1 Ligand as Efficient Homogeneous Catalysts for Sodium Bicarbonate Hydrogenation and Formic Acid Dehydrogenation

The linear tetraphosphine 1,1,4,7,10,10-hexaphenyl-1,4,7,10-tetraphosphadecane (tetraphos-1, P4) was used as its <i>rac</i> and <i>meso</i> isomers for the synthesis of both molecularly defined and in situ formed Fe­(II) complexes. These were used as precatalysts for sodium bicarbonate hydrogenation to formate and formic acid dehydrogenation to hydrogen and carbon dioxide with moderate to good activities in comparison to those for literature systems based on Fe. Mechanistic details of the reaction pathways were obtained by NMR and HPNMR experiments, highlighting the role of the Fe­(II) monohydrido complex [FeH­(<i>rac</i>-P4)]⁺ as a key intermediate. X-ray crystal structures of different complexes bearing <i>rac</i>-P4 were also obtained and are described herein

Bonjean Louis-Bernard

Entrée de dictionnaireDictionnaire historique des juristes français XIIe-XXe siècle

Similar but Different: The Case of Metoprolol Tartrate and Succinate Salts

The solid-state structure and behavior of tartrate (MT-o) and succinate (MS-m) metoprolol salts have been studied with a combined experimental (X-ray diffraction by both single crystal and microcrystalline powder and differential scanning calorimetry) and modeling approach (molecular dynamics and molecular orbital calculations). In spite of their close similarity at the molecular level in the corresponding crystal lattices, calorimetric data suggest for MS-m a slightly greater cohesive energy. In addition and more importantly, they show significantly different “macroscopic” behaviors: MS-m undergoes a reversible anisotropic lattice expansion/contraction upon temperature change and once melted quickly recrystallizes to the starting crystal phase. On the other hand, MT-o expands/contracts isotropically, and upon cooling from the melt gives an amorphous solid, which, at ambient conditions, takes 6 days to completely revert to the starting crystal form. Both findings are relevant in the field of the pharmaceutical drug development; i.e., when the phase purity of these active pharmaceutical ingredients is assessed, discussed, and possibly related to drug product formulations and manufacturing methods

Hierarchy of Supramolecular Arrangements and Building Blocks: Inverted Paradigm of Crystal Engineering in the Unprecedented Metal Coordination of Methylene Blue

The aromatic methylene blue cation (MB⁺) shows unprecedented ligand behavior in the X-ray structures of the trigonal-planar (TP) complexes MBMCl₂ (M = Cu^I, Ag^I). The two isostructural compounds were exclusively synthesized by grinding together methylene blue chloride and MCl solids. Only in the case of AuCl did the technique lead to a different, yet isoformular, Au^I derivative with separated MB⁺ and AuCl₂^– counterions and no direct N–Au linkage. While the density functional theory (DFT) molecular modeling failed in reproducing the isolated Cu and Ag complexes, the solid-state program <i>CRYSTAL</i> satisfactorily provided for Cu the correct TP building block associated with a highly compact π stacking of the MB⁺ ligands. In this respect, the dispersion interactions, evaluated with the DFT functional, provide to the system an extra energy, which likely supports the unprecedented metal coordination of the MB⁺ cation. The feature seems governed by subtle chemical factors, such as, for instance, the selected metal ion of the coinage triad. Thus, the electronically consistent Au^I ion does not form the analogous TP building block because of a looser supramolecular arrangement. In conclusion, while a given crystalline design is generally fixed by the nature of the building block, a peculiarly efficient supramolecular packing may stabilize an otherwise unattainable metal complex

Linear α‑Olefins Obtained with Palladium(II) Complexes Bearing a Partially Oxidized Tetraphosphane

The coordination of Pd­(II) to the 1,3-<i>trans-</i> and 2,3-<i>trans</i>-dioxides and the trioxide of <i>cis</i>,<i>trans</i>,<i>cis</i>-1,2,3,4-tetrakis­(diphenylphosphino)­cyclobutane gave two dinuclear Pd­(II) complexes, which are structural isomers, and a mononuclear complex, respectively. The latter complexes proved to be suitable precatalysts for the oligomerization of ethylene to linear α-olefins (98% selectivity). The different catalytic activity of the structural isomers was shown to depend on the dynamic behavior of the molecular structure

Linear α‑Olefins Obtained with Palladium(II) Complexes Bearing a Partially Oxidized Tetraphosphane

The coordination of Pd­(II) to the 1,3-<i>trans-</i> and 2,3-<i>trans</i>-dioxides and the trioxide of <i>cis</i>,<i>trans</i>,<i>cis</i>-1,2,3,4-tetrakis­(diphenylphosphino)­cyclobutane gave two dinuclear Pd­(II) complexes, which are structural isomers, and a mononuclear complex, respectively. The latter complexes proved to be suitable precatalysts for the oligomerization of ethylene to linear α-olefins (98% selectivity). The different catalytic activity of the structural isomers was shown to depend on the dynamic behavior of the molecular structure

Hierarchy of Supramolecular Arrangements and Building Blocks: Inverted Paradigm of Crystal Engineering in the Unprecedented Metal Coordination of Methylene Blue

The aromatic methylene blue cation (MB⁺) shows unprecedented ligand behavior in the X-ray structures of the trigonal-planar (TP) complexes MBMCl₂ (M = Cu^I, Ag^I). The two isostructural compounds were exclusively synthesized by grinding together methylene blue chloride and MCl solids. Only in the case of AuCl did the technique lead to a different, yet isoformular, Au^I derivative with separated MB⁺ and AuCl₂^– counterions and no direct N–Au linkage. While the density functional theory (DFT) molecular modeling failed in reproducing the isolated Cu and Ag complexes, the solid-state program <i>CRYSTAL</i> satisfactorily provided for Cu the correct TP building block associated with a highly compact π stacking of the MB⁺ ligands. In this respect, the dispersion interactions, evaluated with the DFT functional, provide to the system an extra energy, which likely supports the unprecedented metal coordination of the MB⁺ cation. The feature seems governed by subtle chemical factors, such as, for instance, the selected metal ion of the coinage triad. Thus, the electronically consistent Au^I ion does not form the analogous TP building block because of a looser supramolecular arrangement. In conclusion, while a given crystalline design is generally fixed by the nature of the building block, a peculiarly efficient supramolecular packing may stabilize an otherwise unattainable metal complex

Regioselective Hydromethoxycarbonylation of Terminal Alkynes Catalyzed by Palladium(II)–Tetraphos Complexes

An in situ generated dinuclear palladium hydride complex bearing <i>cis</i>,<i>trans</i>,<i>cis</i>-1,2,3,4-tetrakis­(diphenylphosphanyl)­cyclobutane catalyzed the hydromethoxycarbonylation of terminal alkynes, giving the corresponding branched α,β-unsaturated ester (A) with high regioselectivity

Regioselective Hydromethoxycarbonylation of Terminal Alkynes Catalyzed by Palladium(II)–Tetraphos Complexes

An in situ generated dinuclear palladium hydride complex bearing <i>cis</i>,<i>trans</i>,<i>cis</i>-1,2,3,4-tetrakis­(diphenylphosphanyl)­cyclobutane catalyzed the hydromethoxycarbonylation of terminal alkynes, giving the corresponding branched α,β-unsaturated ester (A) with high regioselectivity