Inorganica Chimica Acta最新文献

{"title":"Co(III) pincer complexes bearing functionalized pyridyl benzothiazoles/(thio)amides for electro- and photo-catalytic hydrogen evolution reaction in acetonitrile","authors":"Crystal M. Thompson ,&nbsp;Elizabeth A. Tonsel-White ,&nbsp;Gabriel M. Mercier ,&nbsp;Garry S. Hanan ,&nbsp;Alvin A. Holder ,&nbsp;Mark A.W. Lawrence","doi":"10.1016/j.ica.2026.123086","DOIUrl":"10.1016/j.ica.2026.123086","url":null,"abstract":"<div><div>Three Co(III) pincer complexes of the general formula [Co(<strong><em>L</em></strong>)I₂(solv)]·(solv)_n (solv = CH₃CH₂OH (<em>n</em> = 0) or H₂O (<em>n</em> = 1) and <strong><em>L</em></strong> = bis-<em>N</em>-(2,5-dimethoxyphenyl)pyridine-2,6-dicarbothioamide (<strong><em>L</em></strong>^{<strong><em>1</em></strong>}), <em>N</em>-(2,5-dimethoxyphenyl)-6-[(2,5-dimethoxyphenyl)carbamothioyl]pyridine-2-carboxamide (<strong><em>L</em></strong>^{<strong><em>2</em></strong>}), and 6-(4,7-dimethoxy-2-benzothiazolyl)-<em>N</em>-(2,5-dimethoxyphenyl)-2-pyridinecarbothioamide (<strong><em>L</em></strong>^{<strong>3</strong>}); were prepared by oxidation of the corresponding Co(II) species using iodine in ethanol to give the Co(III) pincer complexes, <strong>1</strong>–<strong>3</strong>. The Co(III) complexes were shown to be active electrocatalysts for hydrogen evolution reaction at an unmodified glassy carbon electrode in acetonitrile, with Faradaic efficiencies in the range 80–88%, and overpotentials between 490 and 670 mV with acetic acid as the proton source. Faradaic efficiencies ranging from 35 to 65% and overpotentials between 660 and 700 mV were obtained with <em>p</em>-toluene sulfonic acid monohydrate as the proton source. The potential for light-driven hydrogen production of the catalysts were evaluated under blue light (445 nm, 44 mW) under photocatalytic conditions using acetonitrile as solvent, triethanolamine as a sacrificial electron donor, tetrafluoroboric acid (HBF₄, aqueous solution 48%) as a proton donor and ruthenium complex [Ru^II(bpy)₃](PF₆)₂ as a photosensitizer (PS). Complex <strong>1,</strong> which had a κ³-SNS coordination of the ligand, showed the best results, achieving a similar efficiency when compared to the [Co(dmgH)(dmgH₂)Cl₂] reference (within ca 90% of the TON and TOF) with a TON of up to 232 mol_H2.mol_cat⁻¹ and a TOF of up to 13,880 mmol_H2.mol_cat⁻¹.min⁻¹. Complexes <strong>2</strong> and <strong>3</strong> having κ³-ONS and κ³-SNN gave similar results, achieving TON ca. 130 mol_H2.mol_cat⁻¹ and TOF ca. 11,000 mmol_H2.mol_cat⁻¹.min⁻¹, respectively. Complex <strong>1</strong> was able to produce hydrogen over a longer period, suggesting that the κ³-SNS coordination mode improved the lifetime of the Co(III) and the transient species generated in the catalytic cycle.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"594 ","pages":"Article 123086"},"PeriodicalIF":3.2,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146074450","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":"Sustainable catalysis via ferrocene-modified Zr-MOF for solvent-free annulations toward functionalized pyridine heterocycles","authors":"Lokesh Mahavar,&nbsp;Parveen Kumar,&nbsp;Gourav Kumar,&nbsp;Meena Nemiwal","doi":"10.1016/j.ica.2026.123090","DOIUrl":"10.1016/j.ica.2026.123090","url":null,"abstract":"<div><div>The fabrication of bimetallic metal-organic frameworks (MOFs) has emerged as an effective strategy for enhancing both structural stability and catalytic efficiency. In this study, we report the solvothermal synthesis of a zirconium-based framework, Zr@BDC@Fc-MOF, incorporating ferrocene units into the structure. The redox-active ferrocene moieties impart additional functionality, while the Zr-BDC network provides porosity and stability, resulting in a material with improved catalytic properties. The framework was characterized by FT-IR, FE-SEM with EDS mapping, P-XRD, XPS, BET, and TEM, confirming its crystallinity and well-developed porous structure. Zr@BDC@Fc-MOF was subsequently employed as a heterogeneous catalyst for the synthesis of 2-amino-3-cyanopyridine derivatives, affording products in good to excellent yield under ambient conditions. The catalyst exhibited durability and specific catalytic activity, highlighting its potential as a promising platform for sustainable heterocycles synthesis.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"594 ","pages":"Article 123090"},"PeriodicalIF":3.2,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146074532","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":"Mechanistic insights into palladium-catalyzed nucleophilic aromatic fluorination: From early discoveries to recent Design of new Ligands","authors":"Josefredo R. Pliego Jr","doi":"10.1016/j.ica.2026.123081","DOIUrl":"10.1016/j.ica.2026.123081","url":null,"abstract":"<div><div>The development of palladium-catalyzed nucleophilic aromatic fluorination is a noteworthy example of rational ligand design, with theoretical calculations playing a critical role throughout the process. This review presents the historical development of this catalysis, beginning with the first theoretical insights from Yandulov and Tran. In the sequence, the successful design of biaryl monophosphine ligands and experiments performed by Buchwald and coworkers are discussed. The last part is the recent new theoretical insights into the mechanism able to explain the formation of regioisomers, followed by in silico design of more powerful ligands. Along with the text, a close connection between theory and experiments is presented, providing a deep understanding of the mechanism.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"594 ","pages":"Article 123081"},"PeriodicalIF":3.2,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146035665","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":"Mono-, di-, and trinuclear cobalt(III) complexes with a H2salpn derivative: metal-assisted ligand transformation leading to the unusual formation of 2H-1,3-benzoxazine ring","authors":"Seema Nagarajan,&nbsp;Ankit Kumar Srivastava,&nbsp;Samudranil Pal","doi":"10.1016/j.ica.2026.123083","DOIUrl":"10.1016/j.ica.2026.123083","url":null,"abstract":"<div><div>Reaction of Co(ClO₄)₂·6H₂O, <em>N</em>,<em>N′</em>-bis(salicylidene)-2,2-dimethyl-1,3-propanediamine (H₂L, where 2 Hs stand for the two phenolic protons) and NEt₃ in 1:1:2 mol ratio in acetonitrile under aerobic conditions at 298 K produced [Co₂(μ₂-OH)₂(L)₂] (<strong>1</strong>), [Co(L′)₂]ClO₄ (<strong>2</strong>), and [Co₃(μ₃-O)(μ₂-OH)(μ₂-L)₂(L′)]ClO₄·2H₂O (<strong>3</strong>·2H₂O) (HL′ = <em>N</em>-salicylidene-2-methyl-2-(2H-1,3-benzoxazine-2-yl)propylamine, where H denotes the phenolic proton). All three complexes were characterized by ESI-MS, IR and UV–Vis spectroscopic, and X-ray crystallographic measurements. The physical characteristics and the X-ray structures are consistent with the molecular formulas and +3 oxidation state of the metal centers in all three complexes. The structures revealed that one of the two 2-((methyleneimino)methyl)phenol (–CH₂N=CHC₆H₄OH) arms of H₂L is changed to 2H-1,3-benzoxazine, leading to the formation of HL′. The ON₂O-donor (L)²⁻ occupies one axial and three meridional positions in both <strong>1</strong> and <strong>3</strong>·2H₂O, while the transformed ligand (L′)⁻ acts as a facially coordinating N₂O-donor in both <strong>2</strong> and <strong>3</strong>·2H₂O. The metal centers are in distorted octahedral N₂O₄ coordination spheres in <strong>1</strong> and <strong>3</strong>·2H₂O. In contrast, the metal center has a distorted octahedral N₄O₂ coordination environment in <strong>2</strong>. Based on EPR and ESI-MS studies, a mechanism for the observed ligand transformation via metal-assisted alkyl C–H activation followed by C–O bond formation involving a radical intermediate has been proposed.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"594 ","pages":"Article 123083"},"PeriodicalIF":3.2,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146035663","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":"Theranostics of folic acid conjugated cu on Te nanocomposite: Fluorescence sensing, imaging and selective cytotoxicity towards HeLa cells1","authors":"Debashree Das ,&nbsp;Sampurna Bhattacharya ,&nbsp;Shalmali Basu ,&nbsp;Saptydeep Das ,&nbsp;Ujjal Das ,&nbsp;David J. Morgan ,&nbsp;Kamalika Sen","doi":"10.1016/j.ica.2026.123076","DOIUrl":"10.1016/j.ica.2026.123076","url":null,"abstract":"<div><div>A novel folic acid-conjugated composite nanoparticle containing Cu on TeO₂ (FA-NC) was developed via a green synthetic route for targeted cancer theranostics. The nanocomposite exhibited strong fluorescence, enabling sensitive detection of folate receptor-positive HeLa cells with a detection limit of 1.82 × 10³ cells/mL. XPS analyses confirmed the transformation of Cu²⁺ to Cu⁰, and successful surface modification with folic acid was confirmed using Raman spectroscopy. The nanocomposite demonstrated selective imaging of HeLa cells over HaCaT cells, confirming receptor-specific targeting. Furthermore, FA-NC exhibited antiproliferative activity towards HeLa cells with an IC₅₀ of 15 μg/mL. A moderate DNA binding affinity (K_d = 69.2 μM) suggested groove-binding interaction. These results highlight FA-NC as a cost-effective, biocompatible, and dual-functional nanomaterial for simultaneous imaging and therapy of folate receptor-positive cancer cells.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"594 ","pages":"Article 123076"},"PeriodicalIF":3.2,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145975669","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":"Experimental and DFT study of the bis-Schiff base N,N′-pyridyl-imine ligand as a probe for Hg2+ in DMSO solvent","authors":"Sondos A.J. Almahmoud ,&nbsp;Md. Mohon Shek ,&nbsp;Soad S. Alzahrani ,&nbsp;Md. Shakil Hossen ,&nbsp;Wisnu Arfian A. Sudjarwo ,&nbsp;Asma Rshood Alshraim ,&nbsp;A.F.M. Motiur Rahman ,&nbsp;Abdullah Alodhayb ,&nbsp;Shofiur Rahman ,&nbsp;Paris E. Georghiou","doi":"10.1016/j.ica.2026.123080","DOIUrl":"10.1016/j.ica.2026.123080","url":null,"abstract":"<div><div>Mercury contamination in the natural environment and from industrial products and their by-products poses well-documented public health concerns due to its toxicity, persistence, and bioaccumulation. The present study reports on the synthesis and properties of the symmetrical bis-Schiff base ligand, (<em>1E,1E′</em>)-<em>N,N′</em>-(1,4-phenylene)bis(1-(pyridin-2-yl)methanimine) (“<strong>NPIL”</strong>), which exhibits a rapid and distinct colorless to dark yellow colorimetric change upon complexation with Hg²⁺ ions in DMSO media, enabling naked-eye detection. UV–Vis titration in DMSO revealed a strong association constant (<em>K</em>a = 4.8 × 10³ M⁻¹) and a low detection limit (LOD) of 0.027 μM and a quantification limit (LOQ) of 23 μM. The LOD is substantially below Health Canada's recommended value of 2.48 μM. The coordination of Hg²⁺ via the ligand's imine and pyridine nitrogen atoms, as ascertained from ¹H NMR titration experiments in DMSO‑<em>d</em>₆ suggested 2:1, 2:2, and 4:4 metal-to-ligand stoichiometries. Density functional theory (DFT) calculations were performed for several conformations of the host ligand <strong>NPIL</strong> and its complexes with HgCl₂ in DMSO. The binding interaction energies showed that of four possible “<strong><em>A</em></strong>-<strong><em>D</em></strong>\" conformations of <strong>NPIL</strong> examined, a 2:1 HgCl₂ complex with the <em>All-cis</em> <strong>D</strong> conformation (−113.30 kJ·mol⁻¹) is more stable than the 2:1 HgCl₂ complex with the <em>Cis-trans-cis</em> <strong>C</strong> conformation (−111.50 kJ·mol⁻¹) due to strong ligand-to-metal charge transfer and stabilizing noncovalent interactions. The combination of high sensitivity, selective optical response, and its simple synthesis makes <strong>NPIL</strong> a suitable candidate as a cost-effective UV–vis probe for mercury ion detection.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"594 ","pages":"Article 123080"},"PeriodicalIF":3.2,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146035765","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":"Synthesis, characterization and crystal structures of N′-(2-hydroxy-4-methoxybenzylidene)-3-methylbenzohydrazide and it's copper(II), cobalt(III) and zinc(II) complexes with antibacterial activity","authors":"Fu-Lin Mao","doi":"10.1016/j.ica.2026.123094","DOIUrl":"10.1016/j.ica.2026.123094","url":null,"abstract":"<div><div>An aroylhydrazone compound <em>N′</em>-(2-hydroxy-4-methoxybenzylidene)-3-methylbenzohydrazide (H₂L) was prepared and characterized by IR, UV–Vis, ¹H and ¹³C NMR spectra. Reaction of H₂L with copper nitrate, cobalt nitrate and zinc iodide, respectively, afforded three new complexes [Cu₂(HL)₂(ONO₂)₂]∙2H₂O (<strong>1</strong>∙2H₂O), [Co₂L₂(EtOH)₂(OH₂)₂]2NO₃ (<strong>2</strong>), and [Zn₂I₂(HL)₂]∙2EtOH (<strong>3</strong>∙2EtOH). The complexes have been characterized by IR and UV–Vis spectra. Structures of H₂L and the complexes were further confirmed by single crystal X-ray determination. H₂L crystallizes in monoclinic system space group <em>P</em>2₁/<em>c</em>, and the three complexes in triclinic <em>P</em>-1. Single crystal X-ray diffraction analysis reveals that the Cu atoms in <strong>1</strong> and Zn atoms in <strong>3</strong> are in square pyramidal coordination, and the Co atoms in <strong>2</strong> are in octahedral coordination. The compounds were assayed against the bacterial strains <em>Bacillus subtillis</em>, <em>Staphylococcus aureus</em>, <em>Escherichia coli</em>, and <em>Pseudomonas aereuguinosa</em>. The Cu and Zn complexes have effective antibacterial activities.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"594 ","pages":"Article 123094"},"PeriodicalIF":3.2,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146074531","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":"Synthesis, characterization and properties of a series of rare earth 3,5-dichlorobenzoate complexes including 4,4′-dimethyl-2,2′-bipyridine","authors":"Jie Zhao ,&nbsp;Jin-Song Li ,&nbsp;Wei-Yu Zou ,&nbsp;Ju-Wen Zhang ,&nbsp;Bin-Qiu Liu ,&nbsp;Xi-Qiang Tian","doi":"10.1016/j.ica.2026.123093","DOIUrl":"10.1016/j.ica.2026.123093","url":null,"abstract":"<div><div>Under solvothermal conditions of CH₃CH₂OH and H₂O, a series of rare earth-organic complexes [Ln(3,5-DCB)₃(dmbpy)] [Ln = Nd (<strong>1</strong>), Sm (<strong>2</strong>), Eu (<strong>3</strong>), Gd (<strong>4</strong>), Tb (<strong>5</strong>), Dy (<strong>6</strong>), Er (<strong>7</strong>) and Yb (<strong>8</strong>), 3,5-HDCB = 3,5-dichlorobenzoic acid, dmbpy = 4,4′-dimethyl-2,2′-bipyridine] have been synthesized by the reactions of Ln(NO₃)₃·6H₂O with 3,5-HDCB, dmbpy and NaOH. These complexes were characterized by single crystal X-ray diffraction (SCXRD), powder X-ray diffraction (PXRD), elemental analysis (EA), fourier transform infrared (FT-IR) spectrometer, thermogravimetric analysis (TGA) and differential thermoanalysis (DTA). The SCXRD analysis reveals complexes <strong>1</strong>–<strong>8</strong> exhibit two sorts of distinct structures. Complex <strong>1</strong> features a one-dimensional (1D) chain structure, and the adjacent chains are interconnected through the π–π interactions between the dmbpy co-ligands to generate a two-dimensional (2D) supramolecular layer. Complexes <strong>2</strong>–<strong>8</strong> possess discrete dinuclear cluster structures, which can be extended into a three-dimensional (3D) supramolecular framework by the π–π interactions. The fluorescence and fluorescence lifetimes of <strong>2</strong>, <strong>3</strong>, <strong>5</strong> and <strong>6</strong> were studied and the characteristic emission spectra of rare earth ions are observed. The magnetic investigation of <strong>1</strong> and <strong>4</strong>–<strong>8</strong> was conducted and complex <strong>6</strong> displays a slow magnetic relaxation behavior.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"594 ","pages":"Article 123093"},"PeriodicalIF":3.2,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146074530","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":"Noncovalent interaction-driven supramolecular organization in cobalt(III) azide complexes: Experimental and theoretical insights","authors":"Susovan Bera ,&nbsp;Antonio Frontera ,&nbsp;Shouvik Chattopadhyay","doi":"10.1016/j.ica.2025.123057","DOIUrl":"10.1016/j.ica.2025.123057","url":null,"abstract":"<div><div>Three cobalt complexes, <em>[Co</em>^<em>III</em><em>(HL</em>^<em>1</em><em>)</em>_<em>2</em><em>(N</em>_<em>3</em><em>)</em>_<em>2</em><em>]ClO</em>_<em>4</em> (<strong>1</strong>), <em>[Co</em>^<em>III</em><em>(L</em>^<em>2</em><em>)(HL</em>^<em>2</em><em>)(N</em>_<em>3</em><em>)]ClO</em>_<em>4</em> <em>(</em><strong>2</strong><em>) and [Co</em>^<em>III</em><em>(L</em>^<em>3</em><em>)(bzan)(N</em>_<em>3</em><em>)]</em> (<strong>3</strong>), where <em>HL</em>^<em>1</em> <em>=</em> <em>2-(3-(cyclohexylamino)propyliminomethyl)-6-ethoxyphenol, HL</em>^<em>2</em> = <em>2-(2-(dimethylamino)ethyliminomethyl)-6-methoxyphenol, HL</em>^<em>3</em> = <em>2-((2-(diethylamino)ethylimino)methyl)-4,6-dichlorophenol and</em> Hbzan = 1-benzoylacetone<em>,</em> were synthesized and characterized. Complexes <strong>1</strong> and <strong>2</strong> crystallize as cationic mononuclear units with perchlorate counter ions, while complex <strong>3</strong> is a neutral mononuclear species. Structural analyses reveal diverse supramolecular features, including hydrogen bonding, C<img>H⋯O, and C<img>H⋯π interactions. To better understand the role of these noncovalent interactions in directing crystal packing, density functional theory (DFT) calculations were performed. In complex <strong>1</strong>, QTAIM analysis was applied to assess the strength and topology of hydrogen-bonded chains and cation⋯anion⋯cation motifs involving perchlorate. In complexes <strong>2</strong> and <strong>3</strong>, supramolecular dimerization energies were evaluated, revealing dominant C<img>H⋯O and C<img>H⋯π interactions, respectively. Notably, in complex <strong>3</strong>, a comparative study between conventional C<img>H⋯π(arene) and unconventional C<img>H⋯π(azide) interactions was carried out using a model system. Molecular electrostatic potential (MEP) surfaces and QTAIM analyses further support the presence and strength of these interactions. This combined experimental–theoretical approach highlights the structural relevance of weak forces in shaping the solid-state organization of Co(III) complexes.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"594 ","pages":"Article 123057"},"PeriodicalIF":3.2,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145976028","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":"Regioselective hydroboration of alkenes by metal-organic framework confined mononuclear bipyridyl–iron hydride catalyst","authors":"Aditya Kumar ,&nbsp;Rahul Kalita ,&nbsp;Poorvi Gupta,&nbsp;Bharti Rana,&nbsp;Manav Chauhan,&nbsp;Kuntal Manna","doi":"10.1016/j.ica.2026.123082","DOIUrl":"10.1016/j.ica.2026.123082","url":null,"abstract":"<div><div>Hydroboration of alkenes offers an atom-economical method for producing alkylboronates, which are valuable intermediates in organic synthesis. We report the development of a single-site iron(II) hydride species supported by bipyridine-functionalized UiO metal-organic frameworks (bpy-UiO-FeH₂), which serves as a highly active heterogeneous catalyst for selective anti-Markovnikov hydroboration of alkenes. The catalyst yields anti-Markovnikov boronate ester products with up to 94% selectivity at 60 °C and exhibits broad substrate compatibility, accommodating alkenes with diverse substitution patterns and functional groups. In comparison to its homogeneous counterpart (bipyridine–Fe), bpy-UiO-FeH₂ demonstrates superior activity, enhanced selectivity, and excellent recyclability due to the active site isolation of the mononuclear bpy–FeH₂ species within the MOF scaffold, which suppresses intermolecular decomposition pathways. Detailed mechanistic studies on styrene hydroboration, supported by control experiments, spectroscopic analyses, and computational investigations, revealed key insights into the catalytic pathway. This study underscores the potential of MOF-supported earth-abundant metal catalysts for environmentally friendly organic transformations.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"594 ","pages":"Article 123082"},"PeriodicalIF":3.2,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146035764","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}