Russian Journal of Coordination Chemistry最新文献

{"title":"Lanthanide (Sm, Dy) Complexes with the 9,10-Phenanthrenediimine Redox-Active Ligand: Synthesis and Structures","authors":"D. K. Sinitsa,&nbsp;D. P. Akimkina,&nbsp;T. S. Sukhikh,&nbsp;S. N. Konchenko,&nbsp;N. A. Pushkarevsky","doi":"10.1134/S1070328423601012","DOIUrl":"10.1134/S1070328423601012","url":null,"abstract":"<p>The complex formation of the redox-active ligand bis(<i>N</i>,<i>N</i>'-2,6-diisopropylphenyl)-9,10-phenanthrenediimine (^DippPDI) with alkaline metal (Li, K) and lanthanide (Sm, Dy) cations is studied. The reduction of ^DippPDI with an alkaline metal excess affords the dianionic form of the ligand (^DippPDA^2–), which crystallizes with the potassium cation as the coordination polymer [K₂(^DippPDA)(Thf)₃] (Thf is tetrahydrofuran). The reaction of equimolar amounts of the lithium salt with the dianionic form of the ligand and neutral diimine affords the lithium complex with the radical-anion form (^DippPSI^•–) crystallized as [Li(^DippPSI)(Thf)₂]. The samarium(III) complex [SmCp*(^DippPDA)(Тhf)] (<b>I</b>) is formed by the reduction of ^DippPDI with samarocene [Sm<span>({text{Cp}}_{2}^{*})</span>(Thf)₂] (Cp* is pentamethylcyclopentadienide): both the samarium(II) cation and Cp*^– anion are oxidized in the reaction. ^DippPDI does not react with similar ytterbocene. The dysprosium(III) complexes are synthesized by the ion exchange reactions between DyI₃(Thf)_3.5 and potassium or lithium salt with the ^DippPDA^2– dianion. Similar complexes [Dy(^DippPDA)I(Thf)₂] (<b>II</b>^Thf) and [Dy(^DippPDA)I(Thf)(Et₂O)] (<span>({mathbf{I}}{{{mathbf{I}}}^{{{text{E}}{{{text{t}}}_{{text{2}}}}{text{O}}}}})</span>) are formed in the reactions with the potassium salt depending on the solvent used: a THF–hexane or a diethyl ether–<i>n</i>-hexane mixture, respectively. The coordination of the dysprosium cation by the π system of the conjugated fragment of the NCCN ligand is observed in <b>II</b>^Thf, whereas in <span>({mathbf{I}}{{{mathbf{I}}}^{{{text{E}}{{{text{t}}}_{{text{2}}}}{text{O}}}}})</span> this coordination is absent. The reaction with Li₂(^DippPDA) affords the binary complex salt [Li(Тhf)₃(Et₂O)][DyI₂(^DippPDA)(Тhf)] (<b>III</b>, crystallization from a THF–Et₂O mixture). The crystallization from THF gives the [Li(Тhf)₄][DyI₂(^DippPDA)(Thf)] salt (<b>III'</b>) containing the same anion as <b>III</b>. The structures of all new complexes are studied by X-ray diffraction (XRD, CIF files CCDC nos. 2260307–2260313).</p>","PeriodicalId":759,"journal":{"name":"Russian Journal of Coordination Chemistry","volume":"50 1","pages":"73 - 84"},"PeriodicalIF":1.1,"publicationDate":"2024-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140938686","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Influence of the Solvent Nature on the Spin Equilibrium in Solutions of the Cobalt(II) Phenylborate Hexa-n-Butylsulfide Clathrochelate by the Paramagnetic NMR Spectroscopy Data","authors":"D. Yu. Aleshin,&nbsp;V. V. Zlobina,&nbsp;A. S. Belov,&nbsp;Ya. Z. Voloshin,&nbsp;A. A. Pavlov","doi":"10.1134/S107032842360095X","DOIUrl":"10.1134/S107032842360095X","url":null,"abstract":"<p>The spin state of the cobalt(II) phenylborate hexa-<i>n-</i>butylsulfide clathrochelate in solutions is studied by paramagnetic NMR spectroscopy. This cage complex is shown to undergo the temperature-induced spin transition in solvents of different nature (acetonitrile, chloroform, dichloromethane, and benzene). The previously developed method for an analysis of paramagnetic shifts in NMR spectra allows the determination of the thermodynamic parameters (enthalpy and entropy) of the spin equilibrium in the solutions. In spite of the conformational rigidity of the macrobicyclic tris(dioximate) molecules, substantial changes in the electronic structures and spin equilibrium parameters are observed depending on the polarity of the solvent used. This provides opportunities for fine tuning of spin switch characteristics by changing this parameter of the medium.</p>","PeriodicalId":759,"journal":{"name":"Russian Journal of Coordination Chemistry","volume":"50 2","pages":"130 - 136"},"PeriodicalIF":1.1,"publicationDate":"2024-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140938580","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Rhenium(V) Tris(pyrazolyl)borate Thiolate Complex with the Disulfide Bridging Ligand: Synthesis and Structure","authors":"I. V. Skabitskii,&nbsp;S. S. Shapovalov","doi":"10.1134/S1070328423601152","DOIUrl":"10.1134/S1070328423601152","url":null,"abstract":"<p>The reaction of TpReOCl(S^<i>t</i>Bu) (Tp = tris(pyrazolyl)borate anion) with sodium disulfide in dimethoxyethane affords the new binuclear rhenium complex [TpReO(µ-S^<i>t</i>Bu)]₂(µ-S₂) (<b>I</b>). Complex <b>I</b> can also be synthesized by the reaction of TpReO(S^<i>t</i>Bu)₂ with a suspension of manganese(II) bromide in toluene accompanied by the dealkylation of one of the ligands to form one more new complex [TpReO]₂(µ-S₂)(µ-S) (<b>II</b>) containing the bridging sulfide and disulfide ligands. The structures of two crystalline solvates of complex <b>I</b> with dichloromethane containing the molecules with different conformations of the Re₂S₂ fragment (<b>Ia</b> and <b>Ib</b>) and complex <b>II</b> are studied by X-ray diffraction (XRD) (CIF files ССDC nos. 2262677, 2262678, and 2267423 for <b>Ia</b>, <b>Ib</b>, and <b>II</b>, respectively).</p>","PeriodicalId":759,"journal":{"name":"Russian Journal of Coordination Chemistry","volume":"50 2","pages":"156 - 162"},"PeriodicalIF":1.1,"publicationDate":"2024-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140938585","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Composite Materials Based on Biocompatible Metal-Organic Framework and Anthocyanins from Hibiscus sabdariffa for Active Food Packaging","authors":"A. M. Pak,&nbsp;V. V. Novikov","doi":"10.1134/S1070328423601140","DOIUrl":"10.1134/S1070328423601140","url":null,"abstract":"<p>The biocompatible metal-organic framework [Zn₄(GA)₄(H₂O)₄]·4H₂O (H₂GA = glutamic acid) was used as a container for anthocyanins from <i>Hibiscus sabdariffa</i> in composite films based on kappa-carrageenan and hydroxypropyl methylcellulose. The obtained composite materials showed high antioxidant activity and ability to undergo pH-induced color change upon reactions with gaseous products of pathogen development and, hence, possess the potential for practical application as functional materials for food packaging.</p>","PeriodicalId":759,"journal":{"name":"Russian Journal of Coordination Chemistry","volume":"50 2","pages":"113 - 117"},"PeriodicalIF":1.1,"publicationDate":"2024-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140938496","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Potassium, Ytterbium(II), and Samarium(III) Alkoxide Complexes Containing the Tris((2-dimethylaminomethyl)phenyl)methoxide Ligand: Synthesis and Structures","authors":"A. N. Selikhov,&nbsp;G. R. Taranenko,&nbsp;Yu. V. Nelyubina,&nbsp;A. A. Trifonov","doi":"10.1134/S1070328423600961","DOIUrl":"10.1134/S1070328423600961","url":null,"abstract":"<p>The reaction of tris((2-dimethylaminomethyl)phenyl)methanol ((2-Me₂NCH₂C₆H₄)₃COH) with potassium hydride in THF at –35°C affords dimeric alkoxide {[(2-Me₂NCH₂C₆H₄)₃CO]K(THF)}₂ (<b>I</b>) in a yield of 90%. The reaction of compound <b>I</b> with YbI₂(THF)₂ (1 : 1, 25°C) gives the Yb(II) alkoxyiodide complex {[(2-Me₂NCH₂C₆H₄)₃CO]Yb(μ-I)(THF)₂}₂ (<b>II</b>) in a yield of 57%. Complex <b>II</b> in the crystalline state is dimeric due to two bridging iodide ligands. Unlike the Yb(II) compound, the exchange reaction of complex <b>I</b> with SmI₂(THF)₂ (1 : 1, 25°C) in THF followed by the addition of dimethoxyethane (DME) involves the oxidation of the metal to form the trivalent samarium complex [(2-Me₂NCH₂C₆H₄)₃CO]₂SmI (<b>III</b>), which is isolated in a yield of 60%. The molecular structures of the complexes are determined by X-ray diffraction (XRD) (CIF files CCDC nos. 2259700 (<b>I</b>), 2259701 (<b>II</b>), and 2259702 (<b>III</b>)).</p>","PeriodicalId":759,"journal":{"name":"Russian Journal of Coordination Chemistry","volume":"50 2","pages":"96 - 105"},"PeriodicalIF":1.1,"publicationDate":"2024-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140938845","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Redox-Active Tin(IV) Complexes Based on Sterically Hindered Catecholate Ligands","authors":"S. V. Baryshnikova,&nbsp;M. V. Arsen’ev,&nbsp;N. O. Druzhkov,&nbsp;G. K. Fukin,&nbsp;E. V. Baranov,&nbsp;A. V. Piskunov","doi":"10.1134/S1070328423600778","DOIUrl":"10.1134/S1070328423600778","url":null,"abstract":"<p>The oxidative addition of sterically hindered 3,6-dicyclohexyl-<i>o</i>-benzoquinone (L¹), 3,5-di<i>-tert-</i>octyl<i>-o-</i>benzoquinone (L²), 4-<i>tert-</i>octyl<i>-o-</i>benzoquinone (L³), and 3,5-bis(2-phenylpropyl)-<i>o-</i>benzoquinone (L⁴) to tin(II) chloride in THF affords the corresponding tin(IV) catecholate complexes with the general formula RCatSnCl₂·2THF, where Cat is the catecholate fragment; and R is 3,6-<i>с</i>-Hex (<b>I</b>), 3,5-<i>tert</i>-Oct (<b>II</b>), 4-<i>tert</i>-Oct (<b>III</b>), and 3,5-C(Me)₂Ph (<b>IV</b>), regardless of the molar ratio of the starting reactants. The molecular structures of substituted <i>o-</i>benzoquinone L⁴ and complexes <b>I</b> and <b>III</b> in the crystalline form are determined by X-ray diffraction (XRD) (CIF files CCDC nos. 2259370 (L⁴), 2259371 (<b>I</b>), and 2259372 (<b>III</b>)). The oxidation–reduction properties of synthesized compounds <b>I</b>–<b>IV</b> are studied by cyclic voltammetry.</p>","PeriodicalId":759,"journal":{"name":"Russian Journal of Coordination Chemistry","volume":"50 1","pages":"49 - 60"},"PeriodicalIF":1.1,"publicationDate":"2024-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140938584","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Delayed Drug Release Films Based on MIL-100(Fe) Metal-Organic Framework","authors":"A. M. Pak,&nbsp;T. N. Vol’khina,&nbsp;Yu. V. Nelyubina,&nbsp;V. V. Novikov","doi":"10.1134/S1070328423600900","DOIUrl":"10.1134/S1070328423600900","url":null,"abstract":"<p>Biocompatible metal-organic framework MIL-100(Fe) was used as a container for a model hydrophobic active pharmaceutical ingredient, ibuprofen, in composite films based on gelatin, pectin, and kappa-carrageenan. According to powder X-ray diffraction and scanning electron microscopy data, the metal-organic framework retained the crystal structure and its particles were uniformly distributed throughout the hydrocolloid matrix. Testing of the obtained film materials under simulated biological conditions using chromatography–mass spectrometry analysis showed that they are applicable as a dosage form for slow release of active pharmaceutical ingredients.</p>","PeriodicalId":759,"journal":{"name":"Russian Journal of Coordination Chemistry","volume":"50 1","pages":"15 - 20"},"PeriodicalIF":1.1,"publicationDate":"2024-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140938746","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Heteroleptic Zn(II) Halide Complexes with Iodine-Substituted Benzonitriles: Peculiarities of the Halogen Bond in the Solid State","authors":"M. A. Vershinin,&nbsp;A. S. Novikov,&nbsp;M. N. Sokolov,&nbsp;S. A. Adonin","doi":"10.1134/S1070328423700690","DOIUrl":"10.1134/S1070328423700690","url":null,"abstract":"<p>The reactions of zinc(II) bromide with 3- and 4-iodobenzonitriles (3-I-BzCN and 4-I-Bz-CN) afford heteroligand complexes [L₂ZnBr₂] (L = 3-I-BzCN (<b>I</b>) and 4-I-BzCN (<b>II</b>)), whose structures are determined by X-ray diffraction (XRD) (CIF files CCDC nos. 2253175 (<b>I</b>) and 2253176 (<b>II</b>)). Both crystal structures contain halogen bonds I···Br linking the [ZnBr₂L₂] fragments into supramolecular layers (<b>I</b>) or chains (<b>II</b>). The energies of these noncovalent interactions are estimated by quantum-chemical calculations.</p>","PeriodicalId":759,"journal":{"name":"Russian Journal of Coordination Chemistry","volume":"50 1","pages":"1 - 6"},"PeriodicalIF":1.1,"publicationDate":"2024-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140938751","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Stereochemistry of the cis-Tetrafluoro Complexes of Titanium with 1-Ac-2-[Ph2P(O)]-Cyclohexane (1RS,2SR) Stereoisomers in СН2Сl2","authors":"E. G. Il’in,&nbsp;A. S. Parshakov,&nbsp;V. I. Privalov,&nbsp;A. V. Churakov,&nbsp;G. V. Bodrin,&nbsp;E. I. Goryunov","doi":"10.1134/S1070328423700719","DOIUrl":"10.1134/S1070328423700719","url":null,"abstract":"<p>The monodentate phosphoryl-containing ligand 1-Ac-2-[Ph₂P(O)]-cyclohexane (L) bearing two asymmetric carbon atoms is synthesized. The study of its crystal structure shows that L is a racemic mixture of (1R,2S) and (1S,2R) stereoisomers. The complex formation of L with TiF₄ in СН₂Сl₂ is studied by ¹⁹F{¹Н} and ³¹Р{¹Н} NMR spectroscopy. The compositions of the complexes formed in the solution are determined. Racemic and <i>meso-</i>diastereomers of the octahedral complex <i>cis</i>-TiF₄L₂ are formed in the solution as found by an analysis of the ¹⁹F and ³¹Р NMR spectra taking into account the concept of heterotropy of organic compounds. The influence of the optical configuration of stereoisomers of the monodentate ligand coexisting in the coordination sphere of the [MF₄L₂] octahedral tetrafluoro complexes of transition <i>d</i>⁰ metals on the chemical shifts of the fluorine atoms arranged in the <i>trans</i> positions relative to each other is shown. In the <i>meso</i>-diastereomer of <i>cis</i>-TiF₄L₂, this results in a nonequivalence of the fluorine atoms on the F–Ti–F' ordinate of the octahedron, and the spin-spin coupling constant <i>J</i>_FF' = 286.1 Hz is observed in the ¹⁹F{¹H} NMR spectrum.</p>","PeriodicalId":759,"journal":{"name":"Russian Journal of Coordination Chemistry","volume":"50 2","pages":"137 - 144"},"PeriodicalIF":1.1,"publicationDate":"2024-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140938579","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Gold(I) Chloride Complexes with 4-Halo-Substituted Phenyl Isocyanide Ligands","authors":"G. A. Gavrilov,&nbsp;K. N. Davletbaeva,&nbsp;M. A. Kinzhalov","doi":"10.1134/S1070328423600596","DOIUrl":"10.1134/S1070328423600596","url":null,"abstract":"<p>A series of gold(I) monoisocyanide [AuCl(CNC₆H₄-4-X)] (X = Cl (<b>IIa</b>), Br (<b>IIb</b>), I (<b>IIc</b>) and bis<i>-</i>isocyanide [Au(CNC₆H₄-4-X)₂](PF₆) (X = Cl (<b>IIIa</b>), Br (<b>IIIb</b>), I (<b>IIIc</b>) complexes were prepared by the reaction of [AuCl(Tht)] (Tht = tetrahydrothiophene) with the specified isocyanide. The molecular structure of <b>IIa</b>–<b>IIc</b> was established by X-ray diffraction (CCDC no. 2253450 (<b>IIa</b>), 2253447 (<b>IIb</b>), 2253448 (<b>IIc</b>)). The crystals of <b>IIb</b> and <b>IIc</b> are isostructural; they were found to have several types of intermolecular interactions, particularly, C–X⋯Cl–Au halogen bonds, π-hole (C_CNR)···<span>(~{{d}_{{{{z}^{2}}}}})</span>(Au) interactions, and Au⋯Au aurophilic contacts, which form together a two-layer 2D supramolecular polymer. The crystals of <b>IIb</b>, <b>IIc</b> and <b>IIIa</b>, <b>IIIb</b> exhibit phosphorescence at room temperature; compounds <b>IIa</b> and <b>IIIc</b> do not possess luminescent properties; and mechanical grinding of <b>IIa</b>‒<b>IIc</b> and <b>IIIa</b>‒<b>IIIc</b> powders does not change the photophysical properties.</p>","PeriodicalId":759,"journal":{"name":"Russian Journal of Coordination Chemistry","volume":"50 1","pages":"40 - 48"},"PeriodicalIF":1.1,"publicationDate":"2024-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140938567","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}