Russian Journal of Coordination Chemistry最新文献

{"title":"Trinuclear Lutetium(III) Cyclopentadienyl Complex with the 2,2'-Bipyridine Dianion","authors":"D. A. Bardonov,&nbsp;D. M. Roitershtein,&nbsp;D. I. Nasyrova,&nbsp;M. E. Minyaev","doi":"10.1134/S1070328424600165","DOIUrl":"10.1134/S1070328424600165","url":null,"abstract":"<p>The reaction of lutetium cyclopentadienyl anthracenide complex [(C₅H₅)Lu(C₁₄H₁₀)(THF)₂] with 1 equiv. of 2,2'-bipyridine in THF gives the trinuclear complex [{(η⁵-C₅H₅)Lu}₃(μ₂-Bipy)₃] (<b>I</b>), containing a 2,2'-bipyridine dianion. The complex was isolated as a powder with the composition <b>I</b>·0.1(C₁₄H₁₀)·0.8(C₇H₈). The recrystallization from a toluene/hexane mixture resulted in the crystals of <b>I</b>·0.084(C₁₄H₁₀)·0.831(C₇H₈)·0.500(C₆H₁₄), which were studied by X-ray diffraction (monoclinic group <i>P</i>2₁/<i>c</i>; CCDC no. 2311508). Complex <b>I</b> has an unusual μ₂-κ²N¹,N^1':η⁴N¹,C²,C^2',N^1'-bridging coordination of the dianion.</p>","PeriodicalId":759,"journal":{"name":"Russian Journal of Coordination Chemistry","volume":null,"pages":null},"PeriodicalIF":1.1,"publicationDate":"2024-08-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142182695","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":"Isonitrile Coordination to Pincer Iridium Hydrido Chlorides","authors":"E. S. Gulyaeva,&nbsp;E. I. Gutsul,&nbsp;Y. V. Nelyubina,&nbsp;E. S. Osipova,&nbsp;O. A. Filippov,&nbsp;E. S. Shubina,&nbsp;N. V. Belkova","doi":"10.1134/S1070328423601541","DOIUrl":"10.1134/S1070328423601541","url":null,"abstract":"<p>Isonitriles are useful reagents that participate in many cycloaddition or multicomponent reactions of interest in organic synthesis, which are often catalyzed by transition metal complexes. Being good electron donors, RN=C bonds become activated and prone to the nuclephilic attack upon coordination to electrophilic (Lewis acidic) metal centers. Herein we explore the complexation of ^<i>t</i>BuNC to a series of iridium hydrido chlorides supported by benzene-based pincer ligands, (<span>({text{R}}{{{text{-}}}^{{^{t}{text{Bu}}}}}{text{PZCZP}})</span>)IrH(Cl) (<span>({text{R}}{{{text{-}}}^{{^{t}{text{Bu}}}}}{text{PZCZP}})</span> = κ³‑C₆H₃–2,6-(ZP^<i>t</i>Bu₂)₂, where R = H (<b>I</b>–<b>III</b>), EtCO₂–(<b>IV</b>), and Z = CH₂ (<b>I</b>), CH₂, O (<b>II</b>), O (<b>III</b>, <b>IV</b>)), that occurs instantaneously and quantitatively in solution yielding one of possible isomers <b>Ia</b>–<b>IVa</b>. Single crystal X-ray diffraction studies for <b>Ia</b>–<b>IIIa</b> confirmed the apical coordination of isonitrile ligand <i>trans</i> to hydride ligand suggested by NMR studies. Perusal of the structural data suggests stronger binding of ^<i>t</i>BuNC to PCP-supported iridium center in complex <b>Ia</b> in comparison to PCOP/POCOP species <b>IIa</b>–<b>IIIa</b>. Structural data also reveal a distortion in the P–Ir–P arrangement caused by ^<i>t</i>BuNC docking in apical position that is the most noticeable for asymmetric PCOP version <b>IIa</b>. The computational analysis of vibrational frequencies unveils an essential coupling ν_Ir-H and ν_N=С modes that produce two strong bands of similar intensity in the ν_N=C region for <b>Ia</b>. Weaker isonitrile binding in <b>IIa</b>–<b>IVa</b> with shorter N=С and longer N–<span>({{{text{C}}}^{{^{t}{text{Bu}}}}})</span> /Ir–C_CN bonds and a plethora of intramolecular interactions result in a different degree of vibrational mixing for Ir‒H and N=C stretches as well as lead to an intense bands due to a Fermi resonance of low frequency modes involving vibrations of N–C–^<i>t</i>Bu fragment. Thus, the raw experimental IR data should be taken with care as an indicator of RN=С activation, paying attention to the vibrational coupling. An estimation of band position for the “true” (uncoupled) ν_NC vibration gives a small high frequency shift for <b>Ia</b> (+16 cm^<b>–</b>1) but low frequency shifts for other complexes becoming less negative in the order <b>IIa</b>–<b>IIa</b>–<b>IVa</b> (PCOP–POCOP– EtCO₂-POCOP). Overall the results obtained show the influence of the pincer ligand on the complex picture of isonitrile complexes structure and spectra, and suggest that strong binding does not always mean a strong activation.</p>","PeriodicalId":759,"journal":{"name":"Russian Journal of Coordination Chemistry","volume":null,"pages":null},"PeriodicalIF":1.1,"publicationDate":"2024-08-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142182711","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":"Crystal Structure of Tetraammine Zinc(II) Peroxodisulfate and Barium Peroxodisulfate Tetrahydrate","authors":"A. G. Medvedev,&nbsp;T. A. Tripol’skaya,&nbsp;E. A. Mel’nik,&nbsp;P. A. Egorov,&nbsp;N. S. Mayorov,&nbsp;A. A. Mikhaylov,&nbsp;O. Lev,&nbsp;P. V. Prikhodchenko","doi":"10.1134/S1070328423601553","DOIUrl":"10.1134/S1070328423601553","url":null,"abstract":"<p>Zinc(II) tetraammine peroxodisulfate [Zn(NH₃)₄]S₂O₈ (<b>I</b>) and barium peroxodisulfate tetrahydrate BaS₂O₈·4H₂O (<b>II</b>) were synthesized by interaction of an aqueous solution of ammonium peroxodisulfate with a zinc peroxide and barium hydroxide, respectively. The crystal structures (CIF file CCDC nos. 2311248 (<b>I</b>) and 2311249 (<b>II</b>)) were determined by single crystal X-ray diffraction. The crystal structure of <b>I</b>, for which X-ray powder diffraction structural data were previously reported, has been redetermined and clarified. The crystal packing of <b>I</b> consists of hydrogen-bonded chains parallel to the <i>b</i>-axis connected in a three-dimensional structure with H-bonds between adjacent chains. The compound <b>II</b> is coordination polymer with coordination number of barium cation equal to 9. The crystal packing of <b>II</b> consists of channels in which water molecules are held by H-bonds. Compounds <b>I</b> and <b>II</b> were characterized by DTA and TGA revealing thermal stability up to 170 and 90°C.</p>","PeriodicalId":759,"journal":{"name":"Russian Journal of Coordination Chemistry","volume":null,"pages":null},"PeriodicalIF":1.1,"publicationDate":"2024-08-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142182717","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":"Dynamic Magnetic Susceptibility Method in Studies of Coordination Compounds","authors":"N. N. Efimov,&nbsp;K. A. Babeshkin,&nbsp;A. V. Rotov","doi":"10.1134/S1070328424600141","DOIUrl":"10.1134/S1070328424600141","url":null,"abstract":"<p>The measurement of the dynamic magnetic susceptibility is a universal method, which is used for the evaluation of magnetic properties of single molecule magnets by scientists all over the world. An information in the Russian scientific literature that can be useful for practical mastering of this method is presently insufficient. To fill this gap, in this work we present a detailed procedure of a magnetochemical experiment for observing slow magnetic relaxation in coordination compounds of 3<i>d</i>- and 4<i>f</i>-element ions and the complete characterization of the dynamics of the magnetic behavior. Special attention is given to usually omitted but important details related to all stages of studying the magnetic relaxation dynamics. The main variants of sample preparation are described, the logics of the construction of a measuring sequence and the procedure of experimental data processing are discussed, and advantages and drawbacks of some programs of the calculation of magnetic relaxation dynamics data are considered. The main concepts and equations used in experimental data analysis are presented, and the primary conclusions that can be made from the obtained results are proposed.</p>","PeriodicalId":759,"journal":{"name":"Russian Journal of Coordination Chemistry","volume":null,"pages":null},"PeriodicalIF":1.1,"publicationDate":"2024-08-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1134/S1070328424600141.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142182716","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Template Synthesis of the Iron(III) Complex with the Ligands Based on Acylpyrazolonepyridines","authors":"D. D. Strunin,&nbsp;I. A. Nikovskii,&nbsp;A. A. Dan’shina,&nbsp;Yu. V. Nelyubina","doi":"10.1134/S1070328424600645","DOIUrl":"10.1134/S1070328424600645","url":null,"abstract":"<p>The reaction of new bidentate ligand, 1-(5-hydroxy-1-methyl-3-(pyridin-2-yl)-1<i>Н</i>-pyrazol-4-yl)ethan-1-one (L), with iron(III) chloride affords the mononuclear iron(III) complex FeL₂Cl₃, which is characterized by XRD (CIF file CCDC no. 2309481). The intramolecular hydrogen bond between the protonated pyridyl and acetyl groups in ligand L, which exists in the crystal as a zwitterion, provides the formation of rarely met iron complexes in which the β-diketonate fragment coordinates via the η¹ mode. A similar coordination mode along with a possibility of a more favorable η² coordination provides new possibilities for the design of heteropolynuclear compounds of various structures used in the fabrication of molecular devices of data storage and processing.</p>","PeriodicalId":759,"journal":{"name":"Russian Journal of Coordination Chemistry","volume":null,"pages":null},"PeriodicalIF":1.1,"publicationDate":"2024-08-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142182842","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":"Interaction of Lyophilic Zinc(II) Porphyrins with Bovine Serum Albumin","authors":"O. I. Koifman,&nbsp;N. Sh. Lebedeva,&nbsp;E. S. Yurina,&nbsp;Yu. A. Gubarev,&nbsp;S. A. Syrbu,&nbsp;A. N. Kiselev,&nbsp;M. A. Lebedev","doi":"10.1134/S1070328424600244","DOIUrl":"10.1134/S1070328424600244","url":null,"abstract":"<p>Palladium-catalyzed heterylation of monobromophenyl-substituted zinc(II) porphyrin with small heterocycles (benzothiazole, benzoxazole, and N-methylbenzimidazole) was carried out. As a result, unsymmetrical heterylphenyl-substituted zinc(II) porphyrins soluble in organic solvents were obtained. The interaction of heteryl-substituted zinc(II) porphyrins with alpha-helical proteins was studied by spectral methods using bovine serum albumin in aqueous organic solvents. It was found that the titration of the zinc(II) porphyrins with albumin in a sodium phosphate buffer involves a number of equilibria including complexation and aggregation. In the case of porphyrins containing N-methylbenzimidazole and benzoxazole residues, self-aggregation processes initiated by absorption of organic solvent molecules by the protein predominate. It was found that more hydrophobic nature of zinc(II) porphyrin with benzothiazole residue promotes the complex formation with the protein. The photochemical properties of zinc(II) porphyrin with a benzothiazole residue, capacity for the photooxidation of the alpha-helical protein, and the high affinity of protein to this porphyrin make it a promising candidate for the potential applicability for photodynamic inactivation.</p>","PeriodicalId":759,"journal":{"name":"Russian Journal of Coordination Chemistry","volume":null,"pages":null},"PeriodicalIF":1.1,"publicationDate":"2024-08-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142182712","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":"Structural Diversity of Heteroleptic 1,2,4-Triphenylcyclopentadienyl-Bipyridine Complexes of Rare Earth Metals","authors":"D. A. Bardonov,&nbsp;K. A. Lyssenko,&nbsp;S. S. Degtyareva,&nbsp;I. E. Nifant’ev,&nbsp;D. M. Roitershtein","doi":"10.1134/S1070328423601565","DOIUrl":"10.1134/S1070328423601565","url":null,"abstract":"<p>The reaction of triphenylcyclopentadienyl potassium and bipyridine with lanthanum, praseodymium, erbium, lutetium, and scandium chloride tetrahydrofuranates results in the formation of binuclear [Cp^Ph3Ln(Bipy)Cl(μ₂-Cl)]₂ (Ln = La (<b>I</b>), Pr (<b>II</b>)) and mononuclear [Cp^Ph3Ln(Bipy)Cl₂(THF)] (Ln = Er (<b>III</b>), Lu (<b>IV</b>), [Cp^Ph3Sc(Bipy)Cl₂] (<b>V</b>) complexes (Cp^Ph3 = 1,2,4-triphenylcyclopentadienyl, Bipy = bipyridine). The decrease in the REE radius in the series La…Sc results in the formation of mononuclear instead of binuclear complexes and in a decrease in the coordination number of the central ion. The coplanar arrangement of two different π-systems gives rise to stacking interactions between the triphenylcyclopentadienyl ligand and bipyridine. The molecular structure of complexes <b>I</b>–<b>V</b> was established by X-ray diffraction analysis (CCDC nos. 2308609 (<b>I</b>), 2308608 (<b>II</b>), 2308610 (<b>III</b>), 2308611 (<b>IV</b>), 2308607 (<b>V</b>)).</p>","PeriodicalId":759,"journal":{"name":"Russian Journal of Coordination Chemistry","volume":null,"pages":null},"PeriodicalIF":1.1,"publicationDate":"2024-08-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142182713","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":"Half-Sandwich Iminophosphonamide Rhodium Complexes as Highly Efficient Catalysts for Dehydrogenation of Dimethylamine-Borane","authors":"R. I. Nekrasov,&nbsp;T. A. Peganova,&nbsp;A. M. Kal’sin,&nbsp;N. V. Belkova","doi":"10.1134/S1070328424600098","DOIUrl":"10.1134/S1070328424600098","url":null,"abstract":"<p>The dehydrogenation of dimethylamine-borane (DMAB) catalyzed by the iminophosphonamide rhodium(III) complexes [Cp*RhCl{Ph₂P(N–<i>p-</i>Tol)(NR)}] (<b>Iа</b>, R = <i>p-</i>Tol; <b>Ib</b>, R = Me) as well as their in situ formed fulvene [(η⁴-C₅Me₄CH₂)Rh(NPN)] (<b>IIa</b>, <b>IIb</b>) and diene [(η⁴-C₅Me₅H)Rh(NPN)] (<b>IIIa</b>, <b>IIIb</b>) rhodium(I) derivatives is studied. Catalysts <b>IIIa</b> and <b>IIIb</b> turn out to be the most active and demonstrate a TOF activity of 110 (<b>IIIа</b>) and 540 h^–1 (<b>IIIb</b>) at 40°С in toluene. The activity decreases significantly in more polar and coordinating THF. At the same time, the rate of DMAB dehydrogenation by complexes <b>Iа</b> and <b>Ib</b> is lower by 10–30 times, and fulvene complexes <b>Iа</b> and <b>Ib</b> are rapidly deactivated after the active initial period (&lt;20% conversion). The kinetic studies show that the reaction has the first order with respect to the substrate and the catalyst. The model ¹¹В NMR experiments confirm that the reaction proceeds via the intermediate formation of a monomer Me₂N=BH₂, which rapidly dimerizes to (Me₂N–BH₂)₂. The mechanism of DMAB dehydrogenation with the formation of unstable hydride intermediate [Cp*RhH{Ph₂P(N–<i>p-</i>Tol)(NR)}] (<b>IVa</b>, <b>IVb</b>) is proposed on the basis of the preliminarily ³¹Р NMR results and published data.</p>","PeriodicalId":759,"journal":{"name":"Russian Journal of Coordination Chemistry","volume":null,"pages":null},"PeriodicalIF":1.1,"publicationDate":"2024-08-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142182714","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":"Coordination Compounds of Alkali and Rare Earth Metals Based on Centrosymmetric Chlorine-Substituted Bismercaptooxazole. Synthesis, Structure, and Luminescence","authors":"A. F. Rogozhin,&nbsp;V. A. Ilichev,&nbsp;L. I. Silantyeva,&nbsp;T. A. Kovylina,&nbsp;E. A. Kozlova,&nbsp;G. K. Fukin,&nbsp;M. N. Bochkarev","doi":"10.1134/S1070328424600177","DOIUrl":"10.1134/S1070328424600177","url":null,"abstract":"<p>New coordination polymers were synthesized. A ditopic centrosymmetric organic ligand containing oxazole heterocycles, 4,8-dichlorobenzo[1,2d:4,5d']bis(oxazole)-2,6(3H,7H)-dithione (H₂L), was prepared and structurally characterized. It was shown that deprotonated H₂L forms non-luminescent binuclear molecular complexes Li₂L(THF)₆ (<b>I</b>) and Na₂L(DME)₄ (<b>II</b>) with alkali metals, while complexes of H₂L with lanthanides are ionic compounds [Ln(DMSO)₈][L]_1.5 (Ln = Nd (<b>III</b>), Yb (<b>IV</b>)) exhibiting moderate metal-centered emission in the near-infrared (IR) range, despite the absence of coordination of the ligand L to lanthanide ions. The molecular structures of H₂L·2DMSO and <b>I</b>–<b>III</b> were established by X-ray diffraction (CCDC nos. 2320461 (H₂L·2DMSO), 2320462 (<b>I</b>), 2320463 (<b>II</b>), 2320464 (<b>III</b>)).</p>","PeriodicalId":759,"journal":{"name":"Russian Journal of Coordination Chemistry","volume":null,"pages":null},"PeriodicalIF":1.1,"publicationDate":"2024-08-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142182844","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":"Monomeric and Polymeric Cyclopentadienyl Dysprosium Complexes Based on the Acenaphthene-1,2-diimine Ligand","authors":"D. A. Lukina,&nbsp;A. A. Skatova,&nbsp;E. A. Kozlova,&nbsp;I. L. Fedushkin","doi":"10.1134/S1070328424600207","DOIUrl":"10.1134/S1070328424600207","url":null,"abstract":"<p>The reaction of [(Dpp-bian)DyI(Dme)₂] (Dpp-bian is 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene, Dme is CH₃OCH₂CH₂OCH₃) with Cp*K (Cp* is C₅Me₅) in toluene followed by crystallization from benzene affords crystals of the 1D coordination polymer [(Dpp-bian)DyIKCp*]_<i>n</i> (<b>I</b>)·2.6C₆H₆ (26%) and crystals of the monomeric complex [(Dpp-bian)DyCp*(Dme)] (<b>II</b>)·1.5C₆H₆ (12%). The same reaction in 1,2-dimethoxyethane followed by crystallization from benzene makes it possible to isolate only complex <b>II</b>·1.5C₆H₆ in a yield of 48%. The synthesized compounds are characterized by IR and UV spectroscopy and elemental and thermogravimetric analyses. Their molecular structures are determined by XRD (CIF files CCDC nos. 2298407 (<b>I</b>) and 2298408 (<b>II</b>)).</p>","PeriodicalId":759,"journal":{"name":"Russian Journal of Coordination Chemistry","volume":null,"pages":null},"PeriodicalIF":1.1,"publicationDate":"2024-08-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142182710","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}