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Volume 50, Nº 8 (2024)
Articles
Synthesis of (η6-Arene)tricarbonylchromium Complexes of 1,3-Benzodioxanes
Resumo
The reactions of triamminotricarbonylchromium (I) with 1,3-benzodioxane (L1), 2-methyl-1,3-benzodioxane (L2), and 2-phenyl-1,3-benzodioxane (L3) afford new complexes: (η6-C8H8O2)Cr(CO)3 (II), exo- and endo-[2-Me-(η6-C8H7O2)]Cr(CO)3 (III, IV), exo- and endo-[2-Ph-(η6-C8H7O2)]Cr(CO)3 (V, VI), [2-(η6-Ph)-C8H7O2]Cr(CO)3 (VII), and endo-[2-(η6-Ph)]Cr(CO)3-[η6-C8H7O2]Cr(CO)3 (VIII). The structures, compositions, and purity of the synthesized products are proved by UV, IR, and 1H NMR spectroscopy, HPLC, and mass spectrometry. The molecular structures of complexes IV–VI are determined by XRD (CIF files CCDC nos. 2263301 (IV), 2295552 (V), and 2237106 (VI)). A possibility of coordination of the tricarbonylchromium group at different sides of the phenylene ring of ligands L2 and L3 and on the phenyl substituent of ligand L3 is shown.
471-483
2D Coordination Polymers of Zn(II) with Diethylmalonic Acid Dianions and 4,4´-bipyridine: Synthesis and Structures
Resumo
Two new coordination compounds of zinc(II) with diethylmalonic acid anions (Et2mal2–) and 4,4´-bipyridine (4,4´-bipy) are synthesized: {[Zn(H2O)(4,4´-bipy)(Et2mal)]· 0.5C2H5OH·1.5H2O}n (I) and {[Zn4(H2O)2(4,4´-bipy)3(Et2mal)4]·6H2O}n (II). According to the XRD data (CIF files CCDC nos. 2323336 (I) and 2323337 (II)), both compounds are 2D polymers with the sql and bey topology, respectively. The choice of the initial zinc salt and solvent predetermines the compositions and structures of the polymers under similar synthesis conditions.
484-491
Crystal Structure of Lanthanide Salts with 2,4-Dichlorophenoxyacetic Acid
Resumo
Compounds of three types, [LnL3(C2H5OH)] (Ln = Nd (I), Sm (II), Eu (III)), [LnL3(H2O)] (Ln = = Gd (IV), Tb (V)), and [DyL2(NO3)(C2H5OH)2] (VI), were obtained by reactions of lanthanide nitrate with NaL (L– = 2,4-dichlorophenoxyacetate anion) in ethanol. The composition and structure of complexes I–VI were investigated by elemental and thermogravimetric analysis, IR spectroscopy, and X-ray diffraction (nos. 2311578 (I), 2311579 (II), 2311580 (III) 2311581 (IV), 2311582 (VI)). All compounds have a one-dimensional polymer structure in which metal atoms are connected by bridging carboxylate groups. The π–π interactions and intermolecular contacts between the chains give rise to a three-dimensional supramolecular structure.
492-501
The First Example of Dicubane Nickel(II) Complex in the Series of Unsymmetrically Substituted Diketones
Resumo
The first homometal dicubane nickel(II) complex based on unsymmetrically substituted 1,3-diketone (1,1,1-trifluoro-4-(2-methoxyphenyl)butan-2,4-dione) was synthesized and studied by X-ray diffraction using synchrotron radiation (CCDC no. 861889). In the crystal of the complex, nickel atoms are joined into tetrahedra sharing a common vertex with Ni…Ni distances of 3.026–3.127 A; the geometry is completed to a distorted dicubane by μ3-bridging oxygen atoms of the hydroxyl groups. The coordination environment of each metal center is a distorted octahedron, the ligand is deprotonated and performs a bidentate function, forming six-membered chelate rings.
502-509
MethylSulfate Complex (Bu4N)2[Мo6I8(O3SOCH3)6]: Synthesis, Structure, Lability of Ligands, and Phosphorescence
Resumo
New methylsulfate complex (Bu4N)2[Мо6I8(O3SOCH3)6] (I) is synthesized by the reaction of (Bu4N)2[Mo6I8(C≡C–C(O)OCH3)6] with dimethyl sulfate (CH3)2SO4. According to the XRD data, the molybdenum atoms are coordinated by the monodentate methylsulfate ligands. In a DMSO solution, the complex undergoes solvolysis accompanied by the complete substitution of the methylsulfate ligands by the solvent molecules. A powder sample of cluster I luminesces (phosphorescence) with the emission maximum at a wavelength of 620 nm (77 K). Increasing temperature to 300 K results in the shift of the emission maximum to 650 nm and a decrease in the integral intensity by 1.6 times.
510-519
Pseudopolymeric Thallium(I) Di-iso-pentyl Dithiophosphate, [Tl{S2P(O-iso-С5H11)2}]: Synthesis, Structural Organization (Role of Secondary Tl⋅⋅⋅S and Tl⋅⋅⋅O Interactions in Supramolecular Self-Assembly), and Thermal Behavior
Resumo
Crystalline pseudopolymeric thallium(I) di-iso-pentyl dithiophosphate (Dtph), [Tl{S2P(O-iso-С5H11)2}] (I), is synthesized and characterized in detail by single-crystal XRD (CIF file CCDC no. 2296421), simultaneous thermal analysis (STA), multinuclear (1H, 13C, 31P) NMR and IR spectroscopy. Nonequivalent molecules of two types containing Tl(1) and Tl(2) atoms (hereinafter molecules А and В, respectively) are involved (1 : 1) in the formation of the structure of compound I. In both molecules, the S,S´-anisobidentate coordination of the Dtph ligands (Tl–S bond lengths 3.006–3.092 Å) results in the formation of small-size four-membered metallocycles [TlS2P] (a 'butterfly' conformation) with significantly averaged P–S bond lengths (1.966–1.985 Å). Molecules A and B are structurally ordered upon the construction of supramolecular chains of two types (⋅⋅⋅A⋅⋅⋅A⋅⋅⋅A⋅⋅⋅)n and (⋅⋅⋅B⋅⋅⋅B⋅⋅⋅B⋅⋅⋅)n with oppositely directed structural units combined by paired secondary Tl⋅⋅⋅S and Tl⋅⋅⋅O interactions alternating over the chain length. In turn, paired secondary (but weaker) Tl⋅⋅⋅S interactions occur between molecules A and B belonging to two neighboring pseudopolymeric chains. The multiplisity of these interactions provides the formation of double supramolecular ribbons. The thermal behavior of compound I is studied by the STA technique under an argon atmosphere. Thallium(I) tetrathiophosphate Tl3PS4 is identified as the only end product of the thermolysis of compound I. Electron probe microanalysis (EPMA) and scanning electron microscopy (SEM) are used to study the residual substance.
520-532