Vol 43, No 12 (2017)

The reactions of single crystals containing 36-nuclear anionic complexes of cobalt(II), (NBu₄)₈[Co₃₆(H₂O-κO)₁₂(μ₃-OH)₂₀(μ₄-Me₂Mal-κ₂O,O′)₂₄(μ₄-Me₂Mal)₆] · 2.5H₂O ∙ CH₃OH (I), and nickel(II), (NBu₄)₈[Ni₃₆(H₂O-κO)₁₂(μ₃-OH)₂₀(μ₄-Me₂Mal-κ₂O,O′)₂₄(μ₄-Me₂Mal)₆] · 6H₂O ∙ 2C₂H₅OH (II) and (NHEt₃)₃[Ni₃₆(NHEt₃)(H₂O-κO)_12.25(μ₃-OH)₂₀(μ₄-HMe₂Mal-κ₂O,O′)₄(μ₄-Me₂Mal-κ₂O,O′)₂₀(μ₄-Me₂Mal)₆] · 39H₂O (III), with solutions of 1,4-dioxane and a 0.1 M solution of Dabco (Dabco is 1,4-diazabicyclo[2.2.2]octane) in EtOH are studied. An ethanol solution of Dabco dissolves the crystals of the complexes, whereas the insertion of the solvent molecules with single crystal retention (for the cobalt compound containing tetrabutylammonium cation, I), cracking (for the nickel analog, II), or dissolution (for the cobalt complex containing triethylammonium, III) occurs in 1,4-dioxane. The X-ray diffraction analyses show the substitution of the uncoordinated water and ethanol molecules in the starting compound by 1,4-dioxane molecules in the structure of compound I to form (NBu₄)₈[Co₃₆(H₂O-κO)₁₂(μ₃-OH)₂₀(μ₄-Me₂Mal-κ₂O,O′)₂₄(μ₄-Me₂Mal)₆] · 7C₄H₈O₂ (IV), which is accompanied by a change in the conformation and the shift of tetrabutylammonium cations, indicating a possibility of the modification of the 36-nuclear d-metal complexes with the malonic acid derivatives in the solid-phase resolvation reactions (CIF files CCDC no. 1557499 (III) and 1557500 (IV)).

A series of the new tin(IV) complexes based on the 2-hydroxy-4-N-(phenyl)-3,6-di-tert-butyl-p-iminobenzoquinone ligand (LH) containing various hydrocarbon substituents R at the metal atom (R = Me, Et, ⁿBu, ^tBu, and Ph) is synthesized. The structures of the synthesized compounds were determined by elemental analysis, IR spectroscopy, and ¹H and ¹¹⁹Sn NMR spectroscopy. The X-ray diffraction analyses are carried out for the LSnPh³ (I) and L²SnEt² (IV) complexes (CIF files CCDC no. 1557840 (I) and 1557839 (IV)). The main electrochemical characteristics in a solution are obtained for the whole series by cyclic voltammetry.

Syntheses and molecular structures of the heterometallic complexes of nickel cyclopentadienyl triphenylphosphine tellurophenolate with tungsten carbonyls (II and III) (CIF files CCDC nos. 1559733 and 1559734, respectively) are described.

The syntheses of the 2,6-di-tert-butyl-4-(2-hydroxybenzylideneamino)phenolate (L) complexes of Gd (I), Nd (II), Er (III), Yb (IV), Tm (V), Sm (VI), and Tb (VII) are described. The structures of the Gd and Er complexes are determined by X-ray diffraction analysis (CIF files CCDC nos. 1558820 (I) and 1558819 (III)). All synthesized compounds exhibit ligand-centered photoluminescence in a range of 405–485 nm. In addition, the luminescence spectra of solid samples of the neodymium and ytterbium complexes contain narrow bands of f–f transitions characteristic of Nd³⁺ and Yb³⁺ ions.

The sodium salt of heteroleptic molybdenum complex with nitrilotris(methylenephosphonic) acid (NTP), hydroxylamine, and nitrogen(II) oxide Na₃[Mo(NO)(NH₂O){N(CH₂PO₃)₃H}]· 8H₂O was synthesized, isolated, and studied (space group P2₁/c, Z = 4, a = 9.7385(2), b = 10.2542(2), c =21.6517(3) Å, β = 93.7060(10)°). The nitrilotris(methylenephosphonate) ion is monoprotonated at the PO₃ group. The nitrogen atom is deprotonated and coordinates the Mo atom; the NTP denticity is 4. Hydroxylamine is ionized according to the acid type and is bidentate. The Mo–NO group is almost linear (176.31(19)° angle; Mo–N, 1.7599(13) Å; ν(N–O), 1756 cm^–1), the electron density distribution attests to the formation of an Mo–N π-bond. The Mo coordination polyhedron is a distorted pentagonal bipyramid. Two Na ions are coordinated at the vertices of a distorted octahedron and the third one forms a distorted tetrahedral geometry. (CIF file CCDC no. 1543700.)