{"title":"Synthesis, Crystal Structures and Catalytic Oxidation Property of Copper(II) Complexes Derived from 5-Bromo-2-((2-diethylaminoethylimino)methyl)Phenol","authors":"Y. Liu, Q. Yang, S. Wang, R. Liu, Y. Chen, S. Li","doi":"10.1134/S0022476625050178","DOIUrl":"10.1134/S0022476625050178","url":null,"abstract":"<p>Two new copper(II) complexes, [CuBrL] (<b>1</b>) and [CuL(CH<sub>3</sub>COO)] (<b>2</b>), where L is the deprotonated form of the Schiff base 5-bromo-2-((2-diethylaminoethylimino)methyl)phenol (HL), are prepared. The Schiff base and complexes are characterized by IR and UV spectra. In addition, the free Schiff base is characterized by <sup>1</sup>H NMR spectrum. Structures of the complexes are further confirmed by single crystal X-ray determination. The Cu atoms in the complexes are in square planar coordination. The Schiff base ligand coordinates to the Cu atoms through phenolate oxygen, imino nitrogen and amino nitrogen. The bromide and acetate anions in the complexes furnish the square planar coordination. Catalytic property for epoxidation of styrene by the complexes is studied.</p>","PeriodicalId":668,"journal":{"name":"Journal of Structural Chemistry","volume":"66 5","pages":"1051 - 1060"},"PeriodicalIF":1.4,"publicationDate":"2025-06-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145161014","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
D. S. Suslov, M. V. Bykov, Z. D. Abramov, M. V. Pakhomova, T. S. Orlov, A. V. Suchkova, I. A. Ushakov, T. N. Borodina, V. I. Smirnov
{"title":"Structural Features of Cationic Palladium(II) Acetylacetonate Complexes with Dialkylbiarylphosphine Ligands","authors":"D. S. Suslov, M. V. Bykov, Z. D. Abramov, M. V. Pakhomova, T. S. Orlov, A. V. Suchkova, I. A. Ushakov, T. N. Borodina, V. I. Smirnov","doi":"10.1134/S0022476625050191","DOIUrl":"10.1134/S0022476625050191","url":null,"abstract":"<p>The ligand exchange reaction between the [Pd(acac)(MeCN)<sub>2</sub>]BF<sub>4</sub> with the dicyclohexylbiarylphosphine ligands afforded complexes [Pd(acac)(ξPhos)]BF<sub>4</sub> (acac = acetylacetonate; ξPhos = SPhos (dicyclohexyl (2′,6′-dimethoxy[1,1′-biphenyl]-2-yl)phosphine) (<b>1</b>), XPhos (dicyclohexyl(2′,6′-diisopropyl[1,1′-biphenyl]-2-yl)phosphine) (<b>2</b>), RuPhos (dicyclohexyl(2′,6′-diisopropoxy[1,1′-biphenyl]-2-yl)phosphine) (<b>3</b>), and DavePhos (2′-(dicyclohexylphosphino)-<i>N,N</i>-dimethyl-[1,1′-biphenyl]-2-amine) (<b>4</b>)), which were characterized by a variety of spectroscopic techniques. Nevertheless, for the interaction of [Pd(acac) (MeCN)<sub>2</sub>]BF<sub>4</sub> with dicyclohexyl(2′-methyl[1,1′-biphenyl]-2-yl)phosphine (MePhos) the ESI<sup>(+)</sup>-MS data indicated decomposition of [Pd(acac)(MePhos)]BF<sub>4</sub> (<b>5</b>) in acetonitrile. Single-crystal X-ray diffraction study shows that the complexes <b>1</b> and <b>2</b> adopt for the Pd(II) center a typical distorted square planar coordination geometry, with a stabilizing interaction between the Pd and the <i>ipso</i>-carbon of the non-phosphorus-containing aryl ring. The metal–ligand and (complex cation)–anion interactions in the complexes have been examined using the quantum theory of atoms in molecules and by an energy decomposition analysis employing natural orbitals for chemical valence. DFT calculations of <b>1</b>-<b>5</b> using the <i>r</i><sup>2</sup>SCAN-3c methodology together with X-ray diffraction and <sup>13</sup>C NMR data suggested formation of an arenium ion upon complexation for complexes <b>1 -4</b>, whereas for <b>5</b> η<sup>2</sup>-π-interaction were identified through calculations. DFT calculations were additionally employed for detailed assignment of all important bands in the IR spectra of <b>1</b>-<b>4</b>. Furthermore, <b>1</b>-<b>4</b> are suitable precatalysts for the allylation of morpholine with allyl alcohol, achieving a turnover number of 200 moles of 4-allylmorpholine per mole of palladium.</p>","PeriodicalId":668,"journal":{"name":"Journal of Structural Chemistry","volume":"66 5","pages":"1070 - 1094"},"PeriodicalIF":1.4,"publicationDate":"2025-06-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145161176","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A. Yu. Baranov, I. Yu. Bagryanskaya, A. V. Artem’ev
{"title":"Copper(I) Tetrafluoroborate Complexes with bis(2-pyridyl)-t-Butylphosphine","authors":"A. Yu. Baranov, I. Yu. Bagryanskaya, A. V. Artem’ev","doi":"10.1134/S0022476625050087","DOIUrl":"10.1134/S0022476625050087","url":null,"abstract":"<p>The reaction of bis(2-pyridyl)-<i>t</i>-butylphosphine (<b>L</b>) with [Cu(MeCN)<sub>4</sub>]BF<sub>4</sub> in MeCN or CH<sub>2</sub>Cl<sub>2</sub> results in the formation of dinuclear complexes [Cu<sub>2</sub>L<sub>2</sub>](BF<sub>4</sub>)<sub>2</sub> (<b>1</b>) and [Cu<sub>2</sub>L<sub>2</sub>(MeCN)<sub>2</sub>](BF<sub>4</sub>)<sub>2</sub> (<b>2</b>), respectively. In the both complexes, the ligands L act as P,N,N’-bridging ones, holding two Cu atoms in a head-to-tail manner. In the [Cu<sub>2</sub>L<sub>2</sub>]<sup>2+</sup> cations of <b>1</b>, the Cu⋯Cu contact of 2.756 Å is observed, while the similar distances in two independent cations of <b>2</b> are 3.145-3.257 Å. </p>","PeriodicalId":668,"journal":{"name":"Journal of Structural Chemistry","volume":"66 5","pages":"948 - 954"},"PeriodicalIF":1.4,"publicationDate":"2025-06-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145161008","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
V. S. Dmitriev, A. D. Pugachev, V. V. Tkachev, A. N. Utenyshev, D. Yu. Pobedinskaya, N. V. Stankevich, P. B. Chepurnoi, S. M. Aldoshin, A. V. Metelitsa, I. V. Ozhogin
{"title":"Structure Study of the Reaction Product of Formyl-Substituted Spiropyran of 1,3-Benzoxazin-4-One Series with Malonodinitrile","authors":"V. S. Dmitriev, A. D. Pugachev, V. V. Tkachev, A. N. Utenyshev, D. Yu. Pobedinskaya, N. V. Stankevich, P. B. Chepurnoi, S. M. Aldoshin, A. V. Metelitsa, I. V. Ozhogin","doi":"10.1134/S0022476625050063","DOIUrl":"10.1134/S0022476625050063","url":null,"abstract":"<p>Synthesis is reported of new spiropyran based on 1,3-benzoxazin-4-one heterocycle with the vinyl-dicarbonitrile fragment at the 8′ position of the 2<i>H</i>-chromene part of the molecule. The structure of the isolated product is confirmed by NMR and mass spectrometry along with single crystal X-ray diffraction. Intermolecular interactions are stuided in the crystal using Mercury and CrystalExplorer program packages.</p>","PeriodicalId":668,"journal":{"name":"Journal of Structural Chemistry","volume":"66 5","pages":"930 - 938"},"PeriodicalIF":1.4,"publicationDate":"2025-06-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145161013","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Z. V. Rudzis, S. N. Vorobyeva, T. S. Sukhikh, E. Y. Filatov, V. A. Nadolinny, S. N. Berdyugin, S. V. Korenev
{"title":"Double Complex Salt [Pd(NH3)4][VO(H2O)(C2O4)2]·2H2O: Structure and Thermal Properties","authors":"Z. V. Rudzis, S. N. Vorobyeva, T. S. Sukhikh, E. Y. Filatov, V. A. Nadolinny, S. N. Berdyugin, S. V. Korenev","doi":"10.1134/S0022476625050099","DOIUrl":"10.1134/S0022476625050099","url":null,"abstract":"<p>A synthesis of the [Pd(NH<sub>3</sub>)<sub>4</sub>][VO(H<sub>2</sub>O)(C<sub>2</sub>O<sub>4</sub>)<sub>2</sub>]·2H<sub>2</sub>O double complex salt (DCS) is developed and optimized. The compound is characterized by single-crystal and powder XRD, IR spectroscopy, and diffuse reflectance spectroscopy (DRS). Crystal data: <span>(Pbar{1})</span> space group, <i>a</i> = 7.3160(10) Å, <i>b</i> = 8.2700(2) Å, <i>c</i> = 12.9205(2) Å, α = 71.576(10)°, β = 78.477(10)°, γ = 83.844(10)°, <i>Z</i> = 2. An exchange interaction between complex anions is revealed by EPR. The process of DCS thermal decomposition in inert and reducing atmospheres is studied. It is established that the final thermolysis product in the reducing atmosphere is a mixture of the Pd<sub>0.90</sub>V<sub>0.10</sub> solid solution and vanadium(III) oxide. The DRS spectra for the obtained DCS are theoretically calculated.</p>","PeriodicalId":668,"journal":{"name":"Journal of Structural Chemistry","volume":"66 5","pages":"955 - 965"},"PeriodicalIF":1.4,"publicationDate":"2025-06-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145161016","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Synthesis and Structural Characterization of a Novel Ternary Composite Containing xLiFeO2, yLi3V2(PO4)3, AND (1 – x – y)LiCoO2 Composites for Lithium-Ion Batteries (LIBs)","authors":"M. Monajjemi, F. Mollaamin","doi":"10.1134/S0022476625050014","DOIUrl":"10.1134/S0022476625050014","url":null,"abstract":"<p>The objective of this research is to prepare a composite with lower cost and better cyclability than the other cathode materials in lithium-ion battery. A ternary composition with high efficiency and low cost containing LiFeO<sub>2</sub> and Li<sub>3</sub>V<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub> (LVP), was applied instead of pure LiCoO<sub>2</sub> to reduce usage of a percentage Co amount, consequently reducing the cost of cobalt and removing its toxic effect in LIBs. In this study, we synthesized ten samples from mixture of <i>x</i>LiFeO<sub>2</sub>, <i>y</i>Li<sub>3</sub>V<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub>, and (1 – <i>x – y</i>)LiCoO<sub>2</sub> compounds for preparing a suitable cathode electrode with high initial discharge capacity, large cyclability and inexpensive cost instead of traditional cathode materials. As a result by using Raman analysis, X-ray diffraction, and electrochemical analyzing, we found that the Li<sub>1.67</sub>V<sub>0.67</sub> Fe<sub>0.33</sub> Co<sub>0.33</sub> [(PO<sub>4</sub>)<sub>3</sub>,O<sub>2</sub>] composites have high efficiency and best performance in viewpoint of initial capacity, cyclability, charge and discharge capacities among these ten composites.</p>","PeriodicalId":668,"journal":{"name":"Journal of Structural Chemistry","volume":"66 5","pages":"877 - 888"},"PeriodicalIF":1.4,"publicationDate":"2025-06-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145161019","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
T. A. Vaganova, Yu. V. Gatilov, N. A. Kryuchkova, D. P. Pishchur, E. V. Malykhin
{"title":"Competition Between Intermolecular Interactions in the Self-Assembly of Cocrystals of Polyfluorinated Arylenediamines with Crown Ethers: Effect of the Cyano Group","authors":"T. A. Vaganova, Yu. V. Gatilov, N. A. Kryuchkova, D. P. Pishchur, E. V. Malykhin","doi":"10.1134/S0022476625050154","DOIUrl":"10.1134/S0022476625050154","url":null,"abstract":"<p>2,4-Diamino-3,5,6-trifluorobenzonitrile makes cocrystals with macrocyclic 18-crown-6, 15-crown-5, and 12-crown-4 ethers of 4:3, 1:1, and 2:1 stoichiometries respectively. The inability to 1:1 cocrystallization with 18-crown-6 and a nonmonotonic change in the diamine fraction in the cocrystal when the macrocycle size changes distinguish it from a series of structurally similar polyfluoroarylenediamines. In all cocrystals synthesized the cyano group and the polyfluoroaromatic moiety participate in structure-forming interactions (N–H⋯N<sub>cyano</sub> H-bond, π⋯π and <i>p</i>⋯π contacts) supplementing the N–H⋯O<sub>cr</sub> H-bond with crown ether. Quantum chemical DFT computations of the molecular electrostatic potential, binding energies, and topological parameters of the electron density in dimers show a considerable contribution of interactions between aromatic coformer molecules to stabilization of the cocrystal structure. The key factor providing the 1:1 cocrystallization is π-stacking occurring in the cocrystal with 15-crown-5 and is violated when passing to 18-crown-6 due to an increase in the macrocycle size. The structural and quantum chemical analysis performed characterizes the hierarchy of supramolecular synthons as tools to design molecular crystals.</p>","PeriodicalId":668,"journal":{"name":"Journal of Structural Chemistry","volume":"66 5","pages":"1014 - 1034"},"PeriodicalIF":1.4,"publicationDate":"2025-06-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145161177","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
E. A. Ermakova, Yu. A. Golubeva, K. S. Smirnova, L. S. Klyushova, P. E. Savinykh, I. V. Eltsov, E. V. Lider
{"title":"Synthesis and Structures of Ferrocenylmethyl Leucine and a Copper(II) Complex Based on it","authors":"E. A. Ermakova, Yu. A. Golubeva, K. S. Smirnova, L. S. Klyushova, P. E. Savinykh, I. V. Eltsov, E. V. Lider","doi":"10.1134/S0022476625040067","DOIUrl":"10.1134/S0022476625040067","url":null,"abstract":"<p>Ferrocenylmethyl leucine (HL) and a copper(II) complex based on it [Cu(MeOH)LCl]<sub><i>n</i></sub>·<i>n</i>H<sub>2</sub>O (<b>1</b>) are obtained for the first time. The compounds are characterized by the elemental analysis, powder X-ray diffraction, and IR spectroscopy. The ligand structure is confirmed by NMR spectroscopy, and the structure of [Cu(MeOH)LCl]<sub><i>n</i></sub> complex (<b>1a</b>) is determined by the single crystal X-ray diffraction analysis. The complex obtained is a polymeric chain due to the chelate-bridging function of tetradentate L<sup>–</sup> coordinated by oxygen atoms of the carboxylate group and the nitrogen atom of the amino group. The stability of complex <b>1</b> is studied in methanol and an aqueous solution for 48 h. Cytotoxicity of the HL ligand and the copper(II) complex is investigated against MCF7 (breast adenocarcinoma) and MRC5 (lung fibroblast) cell lines. The complex is shown to exhibit the cytostatic activity in the concentration range of 5-50 µM against both cell lines.</p>","PeriodicalId":668,"journal":{"name":"Journal of Structural Chemistry","volume":"66 4","pages":"702 - 711"},"PeriodicalIF":1.2,"publicationDate":"2025-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143913911","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Crystal Structure of Inclusion Compound of Porous Lutetium(III) trans-Thienothiophene-2,5-Dicarboxylate with trans-Cinnamaldehyde","authors":"P. A. Demakov, T. S. Sukhikh, V. P. Fedin","doi":"10.1134/S002247662504002X","DOIUrl":"10.1134/S002247662504002X","url":null,"abstract":"<p>A new inclusion compound of cinnamic aldehyde (cin) based on porous lutetium(III) <i>trans</i>-thienothiophene-2,5-dicarboxylate (ttdc<sup>2–</sup>) metal-organic framework was characterized by means of single-crystal XRD, IR, CHN and TGA methods. The title crystal structure with the formula [Lu<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub> (ttdc)<sub>3</sub>]·2DMF·cin (<b>1</b><sub><b>cin</b></sub>) was derived from the parent MOF [Lu<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>(ttdc)<sub>3</sub>]·4DMF (<b>1</b><sub><b>DMF</b></sub>) upon slow solid-to-liquid solvent exchange. Cinnamal molecules, well-resolved within the structure of rigid coordination network, are hydrogen-bonded to the H atom of coordinated water molecule. Close π⋯π-stacking contacts between the coplanar propene fragments, capable for possible [2+2] cycloaddition reactions, and unusual for cinnamal inclusion compounds, were found between the neighbor guest molecules in the crystal structure.</p>","PeriodicalId":668,"journal":{"name":"Journal of Structural Chemistry","volume":"66 4","pages":"661 - 668"},"PeriodicalIF":1.2,"publicationDate":"2025-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143913883","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A. K. Gukova, V. I. Komlyagina, I. V. Bakaev, E. V. Chekhov, I. S. Fomenko, N. F. Romashev, A. L. Gushchin
{"title":"Palladium(II) Coordination Compound Based on 2-Monophenylhydrazinoacenaphthene-1-One: Synthesis, Structure, and Properties","authors":"A. K. Gukova, V. I. Komlyagina, I. V. Bakaev, E. V. Chekhov, I. S. Fomenko, N. F. Romashev, A. L. Gushchin","doi":"10.1134/S002247662504016X","DOIUrl":"10.1134/S002247662504016X","url":null,"abstract":"<p>The [Pd(phen)(Ph-mhan)](OTf) coordination compound is prepared by the interaction of [Pd(phen)Cl<sub>2</sub>] with 2-monophenylhydrazinoacenaphthene-1-one (Ph-mhan) in the presence of silver triflate. During the reaction, Ph-mhan is deprotonated and is coordinated to the Pd(II) ion as an anion. The obtained compound is characterized by elemental analysis, IR, and <sup>1</sup>H NMR spectroscopy; its crystal structure is determined by XRD; electrochemical and optical properties are studied by cyclic voltammetry and electron absorption spectroscopy, respectively.</p>","PeriodicalId":668,"journal":{"name":"Journal of Structural Chemistry","volume":"66 4","pages":"868 - 876"},"PeriodicalIF":1.2,"publicationDate":"2025-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143913889","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}