Koordinacionnaâ himiâ
ISSN (print): 0132-344X
Media registration certificate: № 0110216 от 08.02.1993
Founders: Kurnakov Institute of General and Inorganic Chemistry of RAS, Russian Academy of Sciences
Editor-in-Chief: Eremenko Igor L., academician RAS, Doctor of Sc., Full Professor
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Vol 51, No 5 (2025)
Articles
Synthesis of Nickel(II) complex with 2,6-dichlorophenyl-substituted pyridylpyrazole
Abstract
The mononuclear nickel(II) complex [L2Ni(CH3OH)]Cl (I) was synthesized by the interaction of new ligand 2-(2,6-dichlorophenyl)-5-(pyridin-2-yl)-2,4-dihydro-3H-pyrazol-3-one (L) with nickel(II) chloride. The solvate of complex I with methanol [L2Ni(CH3OH)]Cl·3CH3OH and the initial ligand L were characterized by X-ray diffraction analysis (CCDC № 2314989 (I), 2314988 (L)). It was observed that ligand L exists in the pyrazolone form based on 1H NMR data, whereas in complex I, it is found in the pyrazolol form according to X-ray diffraction data. Complex I is a unique example of a pyrazolol complex in which the oxygen atom does not engage in coordinating with the transition metal ion to create the coordination polymer.
289-297
The structure of dinuclear fluorooxalatouranylates Rb5[(UO2)2(C2O4)4F] · 2H2O and Ba5[(UO2)2(C2O4)4F]2 · 22H2O
Abstract
Using X-ray diffraction analysis, the structure of the first obtained crystals of Rb5[(UO2)2(C2O4)4F] · 2H2O (I) and Ba5[(UO2)2(C2O4)4F]2 · 22H2O (II) was studied (CCDC № 2392480 (I), 2392481 (II)). The uranium-containing structural units are dinuclear complexes of the same composition [(UO2)2(C2O4)4F]5−, but different structure, which is described by the crystallochemical formulas: A2T11B013M1 (I) and A2B014M2 (II), where A = UO22+, T11 or B01 = C2O42−, and M1 or M2 = F−. The complexes contain crystallographically nonequivalent U(VI) atoms, which are part of uranyl ions and implement pentagonal-bipyramidal coordination. In I, the U(VI) atoms form coordination polyhedra UO2FO4 and UO2O5, and in II — only UO2FO4. In both structures, the dinuclear complexes [(UO2)2(C2O4)4F]5− are connected to form a 3D framework due to the coordination bonds R-O and R-F (R = Rb or Ba), in the voids of which water molecules are located, participating in the formation of a set of hydrogen bonds. The obtained IR spectroscopy results for I and II are consistent with the X-ray diffraction data.
298-305
New 2D coordination polymer of cobalt(II) pivalate with 1,4-diaminobutane: synthesis and thermal properties
Abstract
The reaction of cobalt(II) trimethyl acetate (pivalate) [Co(Рiv)2]n (HРiv = HO2CCMe3) with 1,4-diaminobutane (Dab) in absolute acetonitrile gave a 2D-coordination polymer [Co(Piv)2(Dab)2]n (I) with an admixture of the co-product, but the addition of one equivalent of 2,2´-bipyridine to the reaction mixture made it possible to isolate a single-phase sample of I (according to X-ray diffraction data) with a yield of 78%. The crystal structure of I was determined by X-ray diffraction (CCDC No. 2404406): cobalt(II) atoms in a distorted octahedral environment (CoN4O2) of two monodentate carboxylate groups and four bridging Dab molecules form a layered coordination polymer with a honeycomb-like hcb topology. The thermal behavior of I was studied by synchronous thermal analysis: thermal decomposition leads to the formation of the organic salt (H2Dab)(Piv)2, cobalt(II) pivalate, and the octanuclear complex [Co8O2(Piv)12] — the products were identified by XRD and NMR spectroscopy.
306-314
Synthesis and application of chelated complexes [Zn(L-arg)2(H2O)] and [[Zn(L-arg)2(H2O)](SO4)]2– as chiral selectors
Abstract
By interaction of compounds Zn(II) and L-arginine (L-Arg) the chelated complexes [Zn(L-arg)2(H2O)] (I) and [[Zn(L-arg)2(H2O)](SO4)]2– (II) (L-arg is a deprotonated form of L-Arg) were synthesized. The structure of the obtained complexes was established by IR spectroscopy by comparing the experimental and theoretical IR spectra using quantum chemical modeling. Complexes I and II were studied as chiral selectors of enantioselective voltammetric sensors. It was shown that I exhibits better enantioselective compared to II. By DFT method, it was found that the difference in the exhibited enantioselectivity of complexes I and II can be due of the geometric isomerism of chelate compounds and the peculiarities of the coordination of the obtained complexes with the analyte molecule.
315-326
New nickel pincer complexes based on pentamethylruthenocene
Abstract
New nickel(II) pincer complexes based on the pentamethylruthenocene, NiCl[{2,5-(R2PCH2)2C5H2}Ru(Cp*)] (Cp* = C5Me5, Ia: R = tBu; Ib: R = iPr) were synthesized via a two-step route starting from the 1,3-functionally substituted diol {1,3-(HOCH2)C5H3}Ru(Cp*). In the first step, diol was reacted with dialkylphosphines (tBu2PH, iPr2PH) in acetic acid to give diphosphines {1,3-(R2PCH2)2C5H3}Ru(Cp*) (R = tBu; iPr), which were not isolated in a pure state, but after the removal AcOH, was immediately subjected to cyclometallation with nickel(II) chloride hexahydrate in the presence of pyridine. After all purification procedures, the yields of products Ia and Ib were 31 and 16%, respectively. The complexes were fully characterized by 1H, 31P{1H}, and 13C{1H} NMR spectroscopy. The purity of the products was confirmed by elemental analysis. The structure of complex Ia was established by single-crystal X-ray diffraction (CCDC № 2408463).
327-333
DFT-calculations of 31P NMR chemical shift of σ-donor phosphorus atoms in platinum complexes
Abstract
The scopes and limitations of the calculation approaches for estimating the 31P NMR shifts for σ-donor phosphorus atoms in platinum complexes are analyzed. It is shown that satisfactory accuracy can be obtained only within the fully relativistic formalism (mDKS) framework. Geometry optimization at the PBE0/{6-31+G(d); Pd(SDD)} level is optimal in terms of “price–quality”. The efficiency of the proposed approach is demonstrated for analyzing cis/trans-isomerism in platinum complexes.
334-342
Synthesis and structural features of Co(II) compounds with 3-arylidene-1-pyrroline derivatives and monocarboxylic acids anions
Abstract
A series of acetate and trifluoroacetate compounds of cobalt(II) with derivatives of 3-arylidene-1-pyrrolines (X-L; X = Cl, OH) as N-donor ligands was synthesized. Varying the synthesis and crystallization conditions made it possible to obtain coordination compounds of various compositions and structures: a tetranuclear complex based on a cubane fragment {Co4(OH)4}4– — [Co4(OH)4(Cl–L)4(OAc)4] (I), a 1D-polymer complex [Co(H2O)(Cl–L)2(CF3COO)1.167(OAc)0.833]n (II) or a molecular complex [Co(OH–L)2(OAc)2] (III). The synthesized compounds were characterized by X-ray diffraction, IR spectroscopy and CHN analysis. The structure and crystal packing of the obtained complexes were analyzed in detail, the main structure-forming non-covalent interactions in crystals were identified.
343-352