Inorganica Chimica Acta最新文献

{"title":"Enhancing formate yield through electrochemical CO2 reduction using BiOCl and g-C3N4 hybrid catalyst","authors":"Smritirekha Talukdar ,&nbsp;Manuela Bevilacqua ,&nbsp;Enqi Bu ,&nbsp;Lapo Gabellini ,&nbsp;Lapo Querci ,&nbsp;Juan Josè Delgado ,&nbsp;Matteo Mannini ,&nbsp;Paolo Fornasiero ,&nbsp;Tiziano Montini","doi":"10.1016/j.ica.2024.122395","DOIUrl":"10.1016/j.ica.2024.122395","url":null,"abstract":"<div><div>Electrochemical carbon dioxide (CO₂) reduction with bismuth-based catalysts has been widely investigated in the recent few years. This is due to bismuth’s ability to perform selective electrochemical CO₂ reduction reaction (eCO₂RR) to an important C₁ product, the formate (HCOO^–). However, boosting the performance of such catalysts is a continuous investigation. In this work, enhancing the active sites for eCO₂RR is investigated by forming nanocomposites with graphitic carbon nitride (g-C₃N₄). BiOCl is synthesized by a simple wet-chemical approach in the presence of glycine as size-controlling agent and formed into nanocomposites, which were characterized by Scanning Electron Microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), Infrared (IR) Spectroscopy and N₂ physisorption. Linear Sweep Voltammetry (LSV) in argon and CO₂-saturated atmosphere showed higher current values in the case of CO₂. Chronoamperometries (CA) were recorded at −1.06 V vs Reversible Hydrogen Electrode (RHE) for 5400 s obtaining Faradic Efficiencies (FE) varying in the range of 70–77 % depending on the nanocomposites’ composition. In fact, 52.1 wt% BiOCl/g-C₃N₄ formed the highest yields for formate (with also the highest rate of formation of formate) together with a minimal production of H₂ and CO. The effect of nano-structuration induced by glycine, used as a size-controlling agent, to form nanoplates was crucial: microplates of BiOCl produced without glycine showed an FE of 4 %, reaching 85 % in the case of the nanoplates. Post-electrocatalysis characterization revealed the possible role of Bi₂O₂CO₃ as the active phase for eCO₂RR.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"574 ","pages":"Article 122395"},"PeriodicalIF":2.7,"publicationDate":"2024-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142422554","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":"Heteroleptic complexes of hydrazone Scaffold of picolinoyl N- oxide and 2,4 dihydroxy phenyl moieties; evaluation of antioxidant activity, DNA and protein binding properties and in vitro antiproliferation studies","authors":"Samala Deepa ,&nbsp;Nagaraju Mathangi ,&nbsp;Ravi Mudavath ,&nbsp;Indu Shekhar ,&nbsp;A.V. Aparna ,&nbsp;Ch. Sarala Devi","doi":"10.1016/j.ica.2024.122391","DOIUrl":"10.1016/j.ica.2024.122391","url":null,"abstract":"<div><div>The present study deals with design and synthesis of new mononuclear Cu(II), Co(II), Ni(II) and Zn(II) metal complexes of hydrazone of 2-(2-(2,4-dihydroxybenzylidene)hydrazinecarbonyl)pyridine-1-oxide (H₂L), in a view to study their potential relevance for the biological applications. Structural aspects of the title compound (H₂L) and metal complexes synthesized were evaluated by spectral and analytical methods viz. ¹H NMR, ¹³C NMR, LC-MS, FT-IR, UV–Visible, SEM, EDX, Powder XRD, ESR, TGA and DTA. Ligational properties of H₂L were explored by employing pH metric equilibrium studies for recognizing metal ion binding potential donor sites, and further HyperChem 7.5 software for computing properties of frontier molecular orbitals to ascertain orientation of highest occupied molecular orbitals from which presumably electrons are donated to metal ion in complex formation. The affinity of all title compounds to bind with CT-DNA and the type of interaction, therein have been studied by conducting UV–VIS absorption and fluorescence emission titrations. The protein-binding ability of all metal complexes with two serum proteins (BSA and HSA) were explored by absorption titrations, and further fluorescence titrations for BSA binding were also performed. Antioxidant activity of the title compounds was carried out by the method of free radical scavenging using spectrophotometric technique. Additionally, cytotoxicity of all metal complexes and ligand was measured by CTG cell proliferation assay after treating them with MDA-MB-231 and SKOV-3 cell lines. The cell cycle arrest and apoptosis assay in above cell lines after treatment with title compounds were also investigated by flow cytometry. In addition, molecular docking studies at target CDK2 protein inferred binding affinity of the title compounds through non covalent bonding interactions.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"574 ","pages":"Article 122391"},"PeriodicalIF":2.7,"publicationDate":"2024-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142422549","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":"Green synthesis and antimicrobial evaluation of Ag/TiO2 and Ag/SeO2 Core-Shell nanocomposites using r. Officinalis extract: A combined experimental and docking study","authors":"Yasmeen A.S. Hameed ,&nbsp;Albandary Almahri ,&nbsp;Adel I. Alalawy ,&nbsp;Saham F. Ibarhiam ,&nbsp;Nada D. Alkhathami ,&nbsp;Hadeer Mattar ,&nbsp;Wael M. Alamoudi ,&nbsp;Nashwa M. El-Metwaly","doi":"10.1016/j.ica.2024.122390","DOIUrl":"10.1016/j.ica.2024.122390","url":null,"abstract":"<div><div>The escalating threat of antibiotic resistance necessitates the development of novel, sustainable antibacterial agents. This study investigates the potential of utilizing <em>Rosmarinus officinalis</em> leaf extracts to synthesize Ag/TiO₂ and Ag/SeO₂ nanocomposites. <em>R. officinalis</em> extract, a rich source of phenolic and flavonoid compounds, effectively and safely acts as a reducing and capping agent for the green synthesis of Ag/TiO₂ and Ag/SeO₂ nanocomposites. Characterization of nanocomposites revealed the nanoparticles’ nanoscale size, ranging from 43.34 to 96.58 nm for Ag/TiO₂ and 8.04 to 21.72 nm for Ag/SeO₂. Both types of nanoparticles exhibited a spherical morphology and distinct crystalline structure. The nanoparticles demonstrated significant antibacterial properties against multiple bacterial strains. The effective concentration for antibacterial activity was determined to be 30.99 mg/mL for Ag-TiO₂ and 32.41 mg/mL for Ag-SeO₂ nanoparticles. The surface charge of the nanoparticles was measured to be −14.0 mV for Ag-TiO₂ and −15.4 mV for Ag/SeO₂. Molecular docking simulations investigated the interactions between rosmarinic acid, its derivatives, and the antibiotic cefotaxime with a bacterial protein (e.g., DNA gyrase). These simulations provided insights into the distinct antibacterial mechanisms of these compounds. Briefly, this research highlights the potential of R. officinalis-derived nanocomposites as promising antibacterial agents. The eco-friendly synthesis and promising results pave the way for their development and application in medicine, biochemistry, and environmental fields.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"574 ","pages":"Article 122390"},"PeriodicalIF":2.7,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142326908","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":"Organotin carboxylates with bulky substituents. Synthesis, structure, cytotoxicity and antioxidant activity","authors":"Evgeny Nikitin ,&nbsp;Stanislav Fedorov ,&nbsp;Yulia Gracheva ,&nbsp;Konstantin Lyssenko ,&nbsp;Artem Semykin ,&nbsp;Yury Oprunenko ,&nbsp;Nikita Sobolev ,&nbsp;Dmitrii Mazur ,&nbsp;Ludmila Dubova ,&nbsp;Elena Shevtsova ,&nbsp;Elena Milaeva","doi":"10.1016/j.ica.2024.122388","DOIUrl":"10.1016/j.ica.2024.122388","url":null,"abstract":"<div><div>A series of organotin carboxylates were synthesized and characterized by NMR (¹H, ¹³C, ¹¹⁹Sn) and IR spectroscopy, ESI mass-spectrometry and elemental analysis. The structure of two compounds was resolved directly using X-ray diffraction analysis and unusual heptacoordinated Sn coordination polyhedron was discovered for them. Antioxidant activity of the synthesized compounds was estimated using DPPH, NBT and CUPRAC-tests, lipid peroxidation and lipoxygenase inhibition capacity as well. It was shown that the presence of the hydroxyl group in the aromatic ring of the ligand drastically increases antioxidant potency of the complexes, while not noticeably affecting the antiproliferative properties, which were measured with the standard MTT-test. Moreover, it was shown that derivatives of dibutyl- and di-<em>tert</em>-butyltin exhibit the highest cytotoxicity. Three complexes were put forward as lead compounds and additional apoptosis induction studies were carried out. Noticeable caspase activation was shown for the complexes <strong>4</strong> and <strong>7</strong> thus marking their mode of action. The results obtained show that the complexes herein described are promising antiproliferative agents.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"574 ","pages":"Article 122388"},"PeriodicalIF":2.7,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142357969","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":"Revealing the Unusual behavior of rhenium (I) tricarbonyl complex functionalized with Aza-Macrocycles in response to metal ions","authors":"Belén Gómez–Arteaga ,&nbsp;Alejandra Gómez ,&nbsp;Erick Flores ,&nbsp;Andrés Vega ,&nbsp;Belén Cruz–Piñones ,&nbsp;Fernando Godoy ,&nbsp;Tamara Maldonado","doi":"10.1016/j.ica.2024.122389","DOIUrl":"10.1016/j.ica.2024.122389","url":null,"abstract":"<div><div>Three new rhenium phenanthroline tricarbonyl complexes were synthesized and fully characterized to examine changes in their photophysical properties and spectroscopic behavior in the presence of metal ions. To achieve this, the complexes were designed with modifications in both the phenanthroline and the axial ligand. The 4,7–dichloro–1,10–phenanthroline (Cl₂phen) precursor was functionalized with two units of 1–aza–15–crown–5 (1A15C5) to obtain the complex [Re((A15C5)₂phen)(CO)₃Br] (<strong>1</strong>) with the aim to study the spectroscopic perturbations induced by the binding of the metal ions by this receptor. Interestingly, the rhenium complex <strong>1</strong> shows a particular behavior towards Hg(II) and Pb(II), as a result of the halide abstraction assisted by these metal ions. Additionally, in the presence of Cu(II) the interaction and coordination/binding with the macrocycle cavities is also presumed. The chemical reaction assisted by Hg(II) was confirmed by changes in the absorption, emission and FT–IR spectra of [Re(Cl₂phen)(CO)₃Br] (<strong>2</strong>) in presence of the heavy metal ion. These obtained profiles had similar patterns to the ones shown by the cationic complex [Re(Cl₂phen)(CO)₃(CH₃CN)]PF₆ (<strong>3</strong>). As final confirmation, this last complex was also studied in the presence of metal ions and its spectra remained unaltered.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"574 ","pages":"Article 122389"},"PeriodicalIF":2.7,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142326909","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":"Effect of solution environment on the binding properties of ruthenium(II) complexes [Ru(bim)2(7-CH3-dppz)]2+ and [Ru(bim)2(dppx)]2+ with double-stranded RNA poly(A)·poly(U)","authors":"Keliang Wan ,&nbsp;Lifeng Tan ,&nbsp;Bingxin Wen","doi":"10.1016/j.ica.2024.122387","DOIUrl":"10.1016/j.ica.2024.122387","url":null,"abstract":"<div><div>Two new ruthenium(Ⅱ) complexes containing the same ancillary ligands and different intercalating ligands, [Ru(bim)₂(7-CH₃-dppz)]²⁺ (Ru<strong>1</strong>, bim = 2,2′-biimidazole, 7-CH₃-dppz = 7-methyl-dipyrido-[3,2-<em>a</em>,2′,3′-<em>c</em>]-phenazine) and [Ru(bim)₂(dppx)]²⁺ (Ru<strong>2</strong>, dppx = 7,8-dimethyldipyridophenazine), have been synthesized and characterized in this work, and the interactions of Ru<strong>1</strong> and Ru<strong>2</strong> with double-stranded RNA poly(A)·poly(U) have been comparatively studied under both dilute and molecular crowding conditions. Analysis of spectral titrations and viscosity experiments as well as thermal denaturation experiments suggests that although complexes Ru<strong>1</strong> and Ru<strong>2</strong> in both dilute and molecular crowding solutions bind to poly(A)·poly(U) via intercalation, while the binding and stabilizing effects of the two complexes toward poly(A)·poly(U) under molecular crowding conditions significantly decreases in comparision with those in dilute solutions, suggesting that molecular crowding has a significant weakening effect on the interaction of the two complexes with poly(A)-poly(U). The results obtained will contribute to the understanding of the effects of molecular crowding conditions on the binding and stabilization of double-stranded RNA by metal complexes, in particular Ru(II) complexes.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"574 ","pages":"Article 122387"},"PeriodicalIF":2.7,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142319074","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":"Adenosine triphosphatase synergetic cobalt metal-organic frameworks with enhanced peroxidase-like activity for L-cystine detection","authors":"Liwei Zhu ,&nbsp;Ting Liu ,&nbsp;Zelong Duan,&nbsp;Ling Wang,&nbsp;Xuefan Qiu,&nbsp;Zhihan Sun,&nbsp;Chencan Li","doi":"10.1016/j.ica.2024.122375","DOIUrl":"10.1016/j.ica.2024.122375","url":null,"abstract":"<div><div>The role of metal–organic frameworks (MOFs) in the field of enzyme-like materials is significant, and they have been successfully applied to various peroxidase-like studies involving catalytic oxidation of the substrate 3,3′,5,5′-tetramethylbenzidine (TMB). However, the limited chemical stability of MOFs in aqueous environments hampers their catalytic applications. To address this inherent drawback and enhance the peroxidase-like activity of MOFs, a method involving adenosine triphosphate (ATP) bonding was proposed. In this study, collaborative materials comprising cobalt MOFs (Co-MOFs) and ATP were utilized as model catalysts for TMB catalysis. The presence of ATP significantly improved the catalytic capability of Co-MOFs over a pH range from 3 to 9 and temperatures ranging from 25 to 60 °C. Notably, at pH 7 and 60 °C, the catalytic efficiency increased by approximately 100 times and an impressive enhancement rate of up to 4600% was achieved respectively. This peroxidase-like catalytic system offers a colorimetric detection assay that selectively detects L-cysteine with a limit of detection as low as 76.2 nM. Incorporating ATP into Co-MOFs presents a novel approach for utilizing MOFs in catalysis that is convenient, straightforward, and gentle.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"574 ","pages":"Article 122375"},"PeriodicalIF":2.7,"publicationDate":"2024-09-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0020169324004663/pdfft?md5=cafa3d17bdd1adfba52240d28d67ebd0&pid=1-s2.0-S0020169324004663-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142314669","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":"Three metal–organic compounds based on [SiMo12O40]4-: Synthesis, structures and properties","authors":"Guoqing Lin ,&nbsp;Dai Shi ,&nbsp;Na Wang ,&nbsp;Tong Lu ,&nbsp;Yuguang Zhao","doi":"10.1016/j.ica.2024.122386","DOIUrl":"10.1016/j.ica.2024.122386","url":null,"abstract":"<div><div>Three polyoxometalate-based metal–organic complexes with the ability to treat pollutants in water were obtained under hydrothermal conditions using two flexible bis(triazole) organic ligands, [Cu(bte)₂(H₂O)]₂[SiMo₁₂O₄₀]·2H₂O (<strong>1</strong>), [Cu(btb)₂]₂[SiMo₁₂O₄₀]·H₂O (<strong>2</strong>) and [Cu(btb)₂(H₂O)]₂[SiMo₁₂O₄₀] (<strong>3</strong>) (bte = 1,2-bis(1,2,4-triazol-1-yl)ethane; btb = 1,4-bis(1,2,4-triazol-1-yl)butane). In compound <strong>1</strong>, Cu²⁺ ions are linked by bte into a two-dimensional network layer with [SiMo₁₂O₄₀]^4- anions filled between the layers as guest molecules. In compound <strong>2</strong>, [SiMo₁₂O₄₀]^4- anions act as four-connected ligands to coordinate with Cu²⁺ and fill in the pores of the three-dimensional framework constructed by Cu²⁺ and btb. In compound <strong>3</strong>, [SiMo₁₂O₄₀]^4- anions act as guest molecules to fill the channels of the two-dimensional layer formed by Cu²⁺ and btb. The electrochemical characteristics were studied, such as cyclic voltammetry, electrocatalytic reduction and oxidation of water contaminants, and current sensing of BrO^3-. The photocatalytic degradation of organic dye pollutant MB (methylene blue) performance was also investigated under visible light conditions.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"574 ","pages":"Article 122386"},"PeriodicalIF":2.7,"publicationDate":"2024-09-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0020169324004778/pdfft?md5=3c8e2fb4a2897d752837d9a1d3fda2c1&pid=1-s2.0-S0020169324004778-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142312505","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":"Imidobis(tetraphenylphosphinato)lanthanoid(III) complexes: Synthesis by oxidative protolysis, and redox transmetallation/protolysis, structural studies and Hirshfeld surface analysis","authors":"Shalini Rangarajan ,&nbsp;Owen A. Beaumont ,&nbsp;Maravanji S. Balakrishna ,&nbsp;Glen B. Deacon ,&nbsp;Victoria L. Blair","doi":"10.1016/j.ica.2024.122385","DOIUrl":"10.1016/j.ica.2024.122385","url":null,"abstract":"<div><div>Redox protolysis of [YbCp₂(dme)] (dme = 1,2-dimethoxyethane) by imidotetraphenyldiphosphinate, ({Ph₂PO}₂NH) <strong>LH</strong> yields [YbCp{(Ph₂PO)₂N}₂}(MeCN)] <strong>1</strong> and [Yb{(Ph₂PO)₂N}₃] <strong>2</strong> with the last also obtained by oxidative protolysis of Yb(C₆F₅)₂. The complexes [Ln{(Ph₂PO)₂N}₃] ((Ln = Yb <strong>2</strong>, Er <strong>3</strong>, Gd <strong>4</strong>), [Sm{(Ph₂PO)₂N}₃(MeCN)₃] <strong>5</strong> and [Nd{(Ph₂ PO)₂N}₃] <strong>6</strong> have all been prepared by redox transmetallation/protolysis reactions between Yb, Er, Gd, Sm or Nd metals, bispentafluorophenylmercury and proligand <strong>LH</strong>. Complex <strong>1</strong> is formally eight coordinate with an acetonitrile, cyclopentadienyl (Cp) and two chelating <em>O</em>,<em>O</em>′-(Ph₂PO)₂N ligands, with the MeCN <em>trans</em> to the Cp ring. Complexes <strong>2</strong> and <strong>4·</strong>C₇H₈ are six coordinate monomers with three chelating <em>O</em>,<em>O</em>′ diphosphinate ligands. By contrast <strong>5</strong> is a highly symmetrical nine-coordinate monomer with three acetonitrile and three chelating <em>O</em>,<em>O</em>′-<strong>L</strong> ligands. The three-dimensional Hirshfeld surface (3D-HS) analysis and the two-dimensional fingerprint plots (2D-FP) were quantified for different intermolecular interactions in complexes <strong>2</strong> and <strong>4</strong>.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"574 ","pages":"Article 122385"},"PeriodicalIF":2.7,"publicationDate":"2024-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142326910","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":"Facile CH aryl and OH bonds activation at dirhenium site of [Re2(CO)8(THF)2] complex","authors":"Daniela Maggioni,&nbsp;Pierluigi Mercandelli,&nbsp;Lucia Carlucci","doi":"10.1016/j.ica.2024.122384","DOIUrl":"10.1016/j.ica.2024.122384","url":null,"abstract":"<div><div>The activation of small molecules is a topic of great interest and previously we reported on the easy activation of different types of E<img>H bonds at the dinuclear complex [Re₂(CO)₈(THF)₂] (<strong>1</strong>) where labile THF molecules coordinate to adjacent rhenium(0) atoms. Here we extend the reactivity of <strong>1</strong> reporting on the oxidative addition of benzene and toluene at room temperature to give [Re₂(μ-H)(μ-κ<em>C</em>-Ar)(CO)₈], Ar = −C₆H₅ (<strong>2</strong>) and −C₆H₄Me (<strong>3</strong>). Compound <strong>3</strong> is a new example of μ-κ<em>C</em>-Ar dinuclear rhenium complex and has been obtained as <em>para</em> and <em>meta</em> isomers (<strong>3a</strong>,<strong>b</strong>). It is known from the literature that <strong>2</strong> can activate arenes and heteroarenes via reductive elimination of benzene and oxidative addition of C<img>H bonds to the dinuclear fragment. Here we have studied the reaction of <strong>2</strong> with C₆D₆ and H₂C<img>C(H)Ph and determined the kinetic constants by ¹H NMR (1.4 × 10⁻⁵ s⁻¹ at 308 K and 1.1 × 10⁻⁵ s⁻¹ at 298 K, respectively). The results indicate that the rate-determining step of the reaction is the reductive elimination of benzene, while the oxidative addition is fast. Water and methanol react with <strong>1</strong> in toluene at room temperature to give the hydroxo and methoxo hydrido complexes [Re₂(μ-H)(μ-OR)(CO)₈], R<img>H (<strong>5</strong>) and CH₃ (<strong>6</strong>). On reacting <strong>1</strong> with water in deuterated toluene, and monitoring by ¹H/²H NMR, a preferential deuteration of the hydride site to give [Re₂(μ-D)(μ-OH)(CO)₈] is evidenced. This finding excludes the oxidative addition of water on the dinuclear “Re₂(CO)₈” fragment while supporting a heterolytic addition of water via protonation at the µ-κ<em>C</em>-tolyl group, elimination of toluene and addition of OH⁻. Single crystal X-ray diffraction analyses have been performed for complexes <strong>3a</strong>, <strong>5</strong> and <strong>6</strong> and their solid state structures have been determined. In particular, the crystal structure of <strong>5</strong> results in a new polymorphic form (<strong>5b</strong>) and it is discussed in comparison with the already known one (<strong>5a</strong>).</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"574 ","pages":"Article 122384"},"PeriodicalIF":2.7,"publicationDate":"2024-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142319073","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}