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During the investigation of the binary system Be-Ru two new phases - Be 7 Ru 4 and Be 12 Ru 7 - with similar compositions (63.6 at. % Be and 63.2 at. % Be, respectively), are discovered. They both represent new structural prototypes. The phases are located between Be 2 Ru (Fe 2 P-type structure) and Be 3 Ru 2 (U 3 Si 2 -type structure) in the phase diagram. This explains why their crystal structures, solved and refined from single crystal X-ray diffraction data, are described as 2D intergrowth of Fe 2 P and U 3 Si 2 motives. The calculated electronic density of stats (DOS) reveals pronounced minima in the vicinity of the Fermi level for both compounds. Position-space analysis of chemical bonding exhibits the formation of three- and four-atomic polar bonds, involving both, Ru and Be, atoms, and a strong charge transfer from Be to the more electronegative Ru., (© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

The structural features of the hexagonal layered crystal structure of Be 2 Ru (a=5.7508(3) Å, c=3.0044(2) Å, space group P 6 ‾ ${\bar{6}}$ 2m) were investigated by single crystal X-ray diffraction and transmission electron microscopy (TEM). The residual electron density and high-resolution TEM images show that the real structure can be described as an intergrowth of the main hexagonal matrix of the Fe 2 P type with minor orthorhombic inclusions of its stacking variants. Such atomic arrangement is stabilized by the charge transfer from Be to Ru and by a system of polar three- and four-atomic bonds involving both components. The calculated electronic density of states (DOS) of Be 2 Ru revealed, contrarily to typical intermetallic compounds, a pseudo gap (dip) in the vicinity of the Fermi level. The temperature dependence of the electrical resistivity of Be 2 Ru shows metal behaviour in agreement with the non-zero DOS at the Fermi level., (© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

Mg 29- x Pt 4+ y represents the family of complex intermetallic compounds (complex metallic alloys, CMAs). It crystallizes in the cubic non-centrosymmetric space group F 4̅3 m with a = 20.1068(2) Å and around 400 atoms in a predominantly ordered arrangement. The local disorder around the unit cell origin is experimentally resolved by single-crystal X-ray diffraction in combination with atomic-resolution transmission electron microscopy (TEM, high-angle dark-field scanning TEM) studies. The quantum theory of atoms in molecules-based analysis of atomic charges shows that the unusual mixed Mg/Pt site occupation around the origin results from local charge equilibration in this region of the crystal structure. Chemical bonding analysis reveals for Mg 29- x Pt 4+ y ─rather unexpected for a crystal structure of this size─space-separated regions of hetero- and homoatomic bonds involving three to six partners (bonding inhomogeneity). Pt-containing 11- and 13-atomic units formed by heteroatomic 3 a -, 4 a -, and 5 a -bonds are condensed via edges and faces to large super-tetrahedrons, which are interlinked by Mg-only 6 a -bonds. Spatial separation of the regions with different bonding features is the key difference between the title compound and other CMAs, which are characterized by a predominantly homogeneous distribution of heteroatomic bonds.

The new phase Be 3 Ru crystallizes with TiCu 3 -type structure (space group Pmmn (59), a=3.7062(1) Å, b=4.5353(1) Å, c=4.4170(1) Å), a coloring variant of the hexagonal closest packing (hcp) of spheres. The electronic structure revealed that Be 3 Ru has a pseudo-gap close to the Fermi level. A strong charge transfer from Be to Ru was observed from the analysis of electron density within the Quantum Theory of Atoms in Molecules (QTAIM) framework and polar three- and four-atomic Be-Ru bonds were observed from the ELI-D (electron localizability indicator) analysis. This situation is very similar to the recently investigated Be 5 Pt and Be 21 Pt 5 compounds. The unusual crystal chemical feature of Be 3 Ru is that different charged species belong to the same closest packing, contrary to typical inorganic compounds, where the cationic components are located in the voids of the closest packing formed by anions. Be 3 Ru is a diamagnet displaying metallic electrical resistivity., (© 2022 The Authors. Published by Wiley-VCH GmbH.)

The high incidence of the resistance phenomenon represents one of the most important limitations to the clinical usefulness of cisplatin as an anticancer drug. Notwithstanding the considerable efforts to solve this problem, the circumvention of cisplatin resistance remains a challenge in the treatment of cancer. In this work, the synthesis and characterization of two trans -dichloro(triphenylarsino)( N , N -dialkylamino)platinum(II) complexes ( 1 and 2 ) were described. The trypan blue exclusion assay demonstrated an interesting antiproliferative effect for complex 1 in ovarian carcinoma-resistant cells, A2780cis. Quantitative analysis performed by ICP-AES demonstrated a scarce ability to platinate DNA, and a significant intracellular accumulation. The investigation of the mechanism of action highlighted the ability of 1 to inhibit the relaxation of supercoiled plasmid DNA mediated by topoisomerase II and to stabilize the cleavable complex. Cytofluorimetric analyses indicated the activation of the apoptotic pathway and the mitochondrial membrane depolarization. Therefore, topoisomerase II and mitochondria could represent possible intracellular targets. The biological properties of 1 and 2 were compared to those of the related trans -dichloro(triphenylphosphino)( N , N -dialkylamino)platinum(II) complexes in order to draw structure-activity relationships useful to face the resistance phenotype.

The binary phase Mg 3 Pt 2 was prepared by direct reaction between the elements or by spark-plasma synthesis starting with MgH 2 and PtCl 2 . The compound crystallizes in the monoclinic space group C 2/ c with a = 7.2096(3) Å, b = 7.1912(4) Å, c = 6.8977(3) Å, and β = 106.072(3)° and is isotypic to Eu 3 Ga 2 . Analysis of the electron density within the quantum theory of atoms in molecules shows a significant charge transfer from Mg to Pt in agreement with the electronegativity difference. Further study of the chemical bonding with the electron localizability approach reveals the formation of Pt chains stabilized by a complex system of multicenter interactions involving Mg and Pt species. The metallic character of Mg 3 Pt 2 is confirmed by electronic structure calculations and physical measurements.