Ahmad Sajjadi, Suranjana V. Mayani, Suhas Ballal, Abhayveer Singh, Subhashree Ray, Atreyi Pramanik, Kamal Kant Joshi
{"title":"Design and characterization of Pd@CuFe₂O₄/BPMAEA: a sustainable catalyst for cross-coupling reactions","authors":"Ahmad Sajjadi, Suranjana V. Mayani, Suhas Ballal, Abhayveer Singh, Subhashree Ray, Atreyi Pramanik, Kamal Kant Joshi","doi":"10.1007/s11243-025-00662-6","DOIUrl":"10.1007/s11243-025-00662-6","url":null,"abstract":"<div><p>This study identifies the novel palliated magnetic nanoparticles, Pd@CuFe₂O₄/BPMAEA, as an efficient and sustainable catalyst for Suzuki and Sonogashira cross-coupling reactions. The catalyst is synthesized by integrating palladium onto a magnetic CuFe₂O₄ support, which is functionalized with N,N-bis(2-pyridylmethyl)amine ethylamine (BPMAEA) as a ligand. This strategic design enhances palladium’s catalytic activity and stability while enabling easy separation and recovery of the catalyst from reaction mixtures. Comprehensive characterization techniques, including FT-IR, TEM, XRD, SEM, EDX, and VSM, confirm the successful synthesis of the Pd@CuFe₂O₄/BPMAEA nanoparticles, showcasing favorable structural and magnetic properties. The catalytic performance of the catalyst was assessed under various reaction conditions, demonstrating its remarkable efficiency in promoting both Suzuki and Sonogashira reactions with high yields and selectivity. Notably, the Pd@CuFe₂O₄/BPMAEA catalyst exhibits excellent reusability with minimal activity loss over multiple cycles, highlighting its potential for practical applications in organic synthesis. This research underscores the significance of developing sustainable catalytic systems that enhance reaction efficiency and minimize environmental impact using recoverable materials. Our findings contribute to advancing green chemistry practices in catalysis, paving the way for future innovations in sustainable organic transformations. The catalyst could easily and successfully be recycled up to six times with an E-factor as low as 29.48, a testament to its impressive efficiency and the potential it holds for the future of sustainable catalysis.</p><h3>Graphical abstract</h3>\u0000<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":803,"journal":{"name":"Transition Metal Chemistry","volume":"50 5","pages":"839 - 861"},"PeriodicalIF":1.7,"publicationDate":"2025-07-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145037388","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}
Na-Jing Huang, Guo-Hua Li, Long-Jun Xu, Xiao-Yi Wang
{"title":"Synthesis of AgCu/BNNSs nanocomposites and their significantly enhanced catalytic activity driven by near—infrared photothermal effects","authors":"Na-Jing Huang, Guo-Hua Li, Long-Jun Xu, Xiao-Yi Wang","doi":"10.1007/s11243-025-00664-4","DOIUrl":"10.1007/s11243-025-00664-4","url":null,"abstract":"<div><p>Using a one-step co-reduction method, AgCu bimetallic nanoparticles have been successfully loaded onto few-layer boron nitride nanosheets (BNNSs), which possess high thermal conductivity. The structure and morphology of both the support and the catalyst were characterized using X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and high-resolution transmission electron microscopy (HRTEM). Furthermore, the influence of near-infrared laser irradiation on the catalytic performance of the catalyst was investigated. The study found that the Ag<sub>1</sub>Cu<sub>1</sub>/BNNSs nanocomposite exhibited significant catalytic activity in the reduction of 4-nitrophenol (4-NP). This nanocomposite had an activation energy of only 42.9 kJ/mol and maintained high catalytic activity even after six cycles. Additionally, it was found that near-infrared laser irradiation further enhanced the catalytic activity of the composite material. This enhancement was primarily attributed to the photothermal effect of Ag nanoparticles. Moreover, the BNNSs possess high thermal conductivity. They transferred the photothermal energy generated by the Ag nanoparticles to the external environment, thereby further enhancing the local thermal effect of the catalyst. This work provided a foundation for advancing near-infrared or solar photothermal-enhanced bimetallic nanocomposite catalytic systems.</p></div>","PeriodicalId":803,"journal":{"name":"Transition Metal Chemistry","volume":"50 5","pages":"883 - 894"},"PeriodicalIF":1.7,"publicationDate":"2025-06-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145037166","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":"Research progress in pyrochemical reprocessing of spent nuclear fuel","authors":"Jinrui Wang, Pei Wu, Wentao Zhou, Yong Chen, Liudong Hou, Jing Ma","doi":"10.1007/s11243-025-00660-8","DOIUrl":"10.1007/s11243-025-00660-8","url":null,"abstract":"<div><p>Pyrochemical reprocessing has emerged as a crucial alternative to conventional hydrometallurgical methods for the reprocessing of spent nuclear fuel (SNF), particularly for high-burnup SNF from advanced reactors. Unlike the Plutonium Uranium Recovery by Extraction (PUREX) process, which encounters challenges with high-burnup SNF, pyrochemical reprocessing facilitates the direct processing of short-cooled fuel through electroreduction and electrorefining in molten salt. This review presents the research advancements in electroreduction and electrorefining within the context of pyrochemical reprocessing of SNF, systematically introducing the latest findings across five key areas: the electroreduction of oxide SNF pellets composed of various materials, anode materials, solid cathode materials, liquid cathode materials, and molten salt systems utilized in the electroreduction and electrorefining processes. Finally, the article summarizes the pressing issues currently facing electroreduction and electrorefining and proposes directions for future research.</p></div>","PeriodicalId":803,"journal":{"name":"Transition Metal Chemistry","volume":"50 5","pages":"813 - 827"},"PeriodicalIF":1.7,"publicationDate":"2025-06-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s11243-025-00660-8.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145037335","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Activation of carbon dioxide by electrochemical reduction of molybdenum hexacarbonyl in aprotic solvent: a combined IR spectroelectrochemical and DFT calculation study","authors":"Frederic Gloaguen, Nicolas Le Poul","doi":"10.1007/s11243-025-00659-1","DOIUrl":"10.1007/s11243-025-00659-1","url":null,"abstract":"<div><p>The mechanism of carbon dioxide (CO<sub>2</sub>) activation by the electrochemical reduction of molybdenum hexacarbonyl (Mo(CO)<sub>6</sub>) in dry organic solvent was reinvestigated using IR spectroelectrochemistry (IR-SEC) combined with density functional theory (DFT) calculations. Cyclic voltammetry (CV) and IR-SEC experiments, carried out under inert atmosphere, confirmed that the stable pentacarbonyl dianion [Mo(CO)<sub>5</sub>]<sup>2−</sup> is readily formed at the reduction potential of the hexacarbonyl parent complex. In addition, IR-SEC monitoring of the reduction of Mo(CO)<sub>6</sub> in CO<sub>2</sub>-saturated solution showed an absorption band ascribed to the formation of bicarbonate (HCO<sub>3</sub><sup>−</sup>), but no signs for the formation of formate (HCO<sub>2</sub><sup>−</sup>) or oxalate (C<sub>2</sub>O<sub>4</sub><sup>2−</sup>). These experimental results were rationalized by DFT calculations on the coordination mode of CO<sub>2</sub> to [Mo(CO)<sub>5</sub>]<sup>2−</sup>. Indeed, no stable structure could be calculated for the η<sup>1</sup>-OCO isomer, whereas the optimized structure of the η<sup>2</sup>-CO<sub>2</sub> isomer was calculated to be energetically less stable than that of the η<sup>1</sup>-CO<sub>2</sub> isomer, the latter being identified as a key intermediate for the selective formation of carbon monoxide (CO) and water (H<sub>2</sub>O) upon O-protonation of the CO<sub>2</sub>-adduct. This catalytic behavior is discussed here in terms of Mulliken atomic charge redistribution over the CO<sub>2</sub> binding and activation processes, and compared with what was previously reported for tetracarbonyl Mo-diimine complexes, where diimine ligands display “redox non-innocent” properties.</p></div>","PeriodicalId":803,"journal":{"name":"Transition Metal Chemistry","volume":"50 5","pages":"803 - 812"},"PeriodicalIF":1.7,"publicationDate":"2025-06-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145037334","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}
Alaa Nihad Tuama, Khalid Haneen Abass, Bahaa H. Rabee, Raad Shaker Alnayl, Laith H. Alzubaidi, Zahraa N. Salman, Mohd Arif bin Agam
{"title":"Electron donors' approach to enhance photocatalytic hydrogen production of TiO2: a critical review","authors":"Alaa Nihad Tuama, Khalid Haneen Abass, Bahaa H. Rabee, Raad Shaker Alnayl, Laith H. Alzubaidi, Zahraa N. Salman, Mohd Arif bin Agam","doi":"10.1007/s11243-025-00663-5","DOIUrl":"10.1007/s11243-025-00663-5","url":null,"abstract":"<div><p>A sustainable solution to the intermittent nature of solar energy is using photocatalysts powered by sunlight to produce hydrogen from water, which offers a green substitute for fossil fuels. As the most promising semiconductor material for photocatalytic water splitting, TiO<sub>2</sub>-based nanomaterials have received increasing attention from researchers in academia and industry in recent years. However, challenges remain to be addressed, such as a large bandgap, electron–hole recombination, preparation imperfections, and the possibility of excessive H2 production. Several approaches, including the addition of electron donors, doping, and defect engineering have been studied to overcome these constraints and enhance TiO<sub>2</sub> performance. Here, we provide a concise overview of the various techniques used to synthesize TiO<sub>2</sub>-nanostructured photocatalyst. The present study also provides an overview of recent studies on the various factors influencing the photocatalytic process that produces H2 through water splitting. Important properties of photocatalysts include surface chemistry, particle size, pH, temperature, light source, electron donors, band gap, and the synthesis of both pure and doped TiO<sub>2</sub> photocatalyst materials are also discussed. Additionally, a comparative hydrogen generation rate is tabulated to get insight into the most effective synthesis process and type of TiO<sub>2</sub> for effective photocatalysis.</p><h3>Graphical abstract</h3>\u0000<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":803,"journal":{"name":"Transition Metal Chemistry","volume":"50 5","pages":"863 - 882"},"PeriodicalIF":1.7,"publicationDate":"2025-06-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145037206","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 growth, characterization and photoluminescence studies of a new coordination compound of Ni(II) with nicotinamide and 1,5-naphthalenedisulfonic acid","authors":"Arya Mukundan, S. Shibu Prasad","doi":"10.1007/s11243-025-00665-3","DOIUrl":"10.1007/s11243-025-00665-3","url":null,"abstract":"<div><p>A new coordination compound of Ni(II) with nicotinamide (Nic) and 1,5-naphthalenedisulfonic acid (H<sub>2</sub>NDS) of formula {[Ni(Nic)<sub>2</sub>(H<sub>2</sub>O)<sub>4</sub>]NDS}.3H<sub>2</sub>O (<b>NNDSN</b>) has been prepared by gel diffusion technique. SXRD data show that the compound crystallizes in triclinic space group <i>P</i> <span>(overline{1 })</span>. In the crystal structure, the Ni(II) ion is coordinated with two nicotinamide units through the nitrogen atom of pyridine ring and four water molecules. The distorted octahedral geometry of the six coordinate Ni(II) compound can be understood from the <span>(angle)</span> N–Ni–O (ranges from 86.59(7) to 93.41(7)°), <span>(angle)</span> O–Ni–O (88.63(7)° and 91.37(7)°) and difference in bond distances of Ni–O (2.0505(15) and 2.0533(16) Å) and Ni–N (2.1323(17) Å). 1,5-Naphthalenedisulfonate ions present in the crystal lattice balance the charge of Ni(II) ions. In the crystal structure, both coordinated and lattice water molecules, sulfonate groups of 1,5-naphthalenedisulfonate ions and NH<sub>2</sub> group of nicotinamide molecules are involved in intermolecular hydrogen bonding. These interactions further stabilize the crystal structure. FT-IR spectral studies show that SO<sub>3</sub><sup>−</sup> group of 1,5-naphthalenedisulfonate ion, C = O and NH<sub>2</sub> groups of nicotinamide molecule are not involved in coordinate bond formation. In the UV–vis spectrum, the peaks corresponding to <sup>3</sup>A<sub>2g</sub> → <sup>3</sup>T<sub>1g</sub> (P) and <sup>3</sup>A<sub>2g</sub> → <sup>3</sup>T<sub>1g</sub> (F) transitions are observed at λ<sub>max</sub> of 388 and 685 nm respectively. TG/DTG studies show that the crystal structure is stable up to 102 °C and the decomposition to NiO takes place through six stages. Photoluminescence studies show that the emission intensity of <b>NNDSN</b> can be quenched by Fe<sup>3+</sup> ions. This method can be used for the sensing of Fe<sup>3+</sup> ion at micro level concentration.</p></div>","PeriodicalId":803,"journal":{"name":"Transition Metal Chemistry","volume":"50 5","pages":"895 - 903"},"PeriodicalIF":1.7,"publicationDate":"2025-06-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145037472","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":"Optimizing catalytic performance of ReS2 thin films: development of Re(1−x)WxS2 alloys for enhanced hydrogen evolution via aerosol-assisted CVD","authors":"Naktal Al-Dulaimi, Mundher Al-Shakban, Inigo Yrezabal, Andinet Ejigu","doi":"10.1007/s11243-025-00661-7","DOIUrl":"10.1007/s11243-025-00661-7","url":null,"abstract":"<div><p>Transition metal dichalcogenides (M = Mo, W, Re) have gained significant attention for electrocatalytic applications in renewable energy due to their unique layered structures. However, their catalytic activity is often limited by the inert nature of basal planes, with active sites primarily located along the edges. In this study, we employed doping as a strategy to enhance the catalytic performance of Re<sub>(1−<i>x</i>)</sub>W<sub><i>x</i></sub>S<sub>2</sub> alloys by increasing the density of active sites. Using Re<sub>2</sub>(<i>µ</i>-S)<sub>2</sub>(S<sub>2</sub>CNEt<sub>2</sub>)<sub>4</sub> (1) and WS<sub>3</sub>(S<sub>2</sub>CNEt<sub>2</sub>)<sub>2</sub> (2) as precursors, thin films were synthesized via aerosol-assisted chemical vapor deposition at 500 °C. Comprehensive characterization using powder X-ray diffraction, Raman spectroscopy, inductively coupled plasma optical emission spectroscopy, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and transmission electron microscopy (TEM) confirmed the successful formation of Re<sub>(1−<i>x</i>)</sub>W<sub><i>x</i></sub>S<sub>2</sub> alloys. TEM analysis revealed a phase transition from 1T to 2H at W concentrations between 22.6 and 30.8%, indicating a structural evolution from the ReS<sub>2</sub> (1T) to WS<sub>2</sub> (2H) phase. Catalytic testing of both bulk and exfoliated materials in hydrogen evolution demonstrated that doping-induced structural modifications led to a higher density of catalytically active sites, significantly enhancing performance. These findings underscore the role of doping in tailoring the electronic and structural properties of TMDCs to optimize their catalytic efficiency, paving the way for their broader application in sustainable energy technologies.</p></div>","PeriodicalId":803,"journal":{"name":"Transition Metal Chemistry","volume":"50 5","pages":"829 - 837"},"PeriodicalIF":1.7,"publicationDate":"2025-06-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145037053","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":"Preparation and characterization of Cu3(PO4)2 as catalyst for Fenton-like reactions","authors":"D. Meziani, Y. Roumila, I. Belkhettab, M. Trari","doi":"10.1007/s11243-025-00658-2","DOIUrl":"10.1007/s11243-025-00658-2","url":null,"abstract":"<div><p>The removal of organic pollutants, particularly textile dyes, using green and efficient methods is a key focus for researchers addressing environmental pollution. Advanced oxidation processes (AOPs), especially the Fenton-like process, have garnered significant attention for their ability to break down recalcitrant organic molecules into harmless byproducts, namely water and carbon dioxide, through the generation of hydroxyl radicals (<sup>·</sup>OH). In this study, a heterogeneous Fenton-like catalyst, copper phosphate Cu<sub>3</sub>(PO<sub>4</sub>)<sub>2</sub>, was synthesized in the presence of oxalate to achieve a unique morphology. The material was characterized by various physicochemical techniques, including TG, XRD, SEM, UV–Vis, XPS, photoluminescence (PL), and electrochemical impedance spectroscopy (EIS), to evaluate its potential for degrading Basic Yellow 28 (BY-28), a common organic dye of the textile industry. The degradation process was conducted at neutral pH with a BY-28 dye concentration of 20 mg L<sup>−1</sup> and a catalyst dose of 1 g L<sup>−1</sup>. The catalytic activity is attributed to the high concentration of Cu<sup>2+</sup> on the catalyst surface, which efficiently generates <sup>•</sup>OH radicals by activating hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>).</p></div>","PeriodicalId":803,"journal":{"name":"Transition Metal Chemistry","volume":"50 5","pages":"793 - 802"},"PeriodicalIF":1.7,"publicationDate":"2025-06-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145037052","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}
Cihang Kang, Lian Yang, Yuan Zheng, Zhong Zhang, Shuaixue Yan, Guocheng Liu, Xiuli Wang
{"title":"A high-performance bifunctional catalyst with a 2D [TeMo6O24]-based framework for efficient CEES oxidation and electrochemical sensing of Cu2+","authors":"Cihang Kang, Lian Yang, Yuan Zheng, Zhong Zhang, Shuaixue Yan, Guocheng Liu, Xiuli Wang","doi":"10.1007/s11243-025-00657-3","DOIUrl":"10.1007/s11243-025-00657-3","url":null,"abstract":"<div><p>Under hydrothermal conditions, a two-dimensional (2D) Anderson-type polyoxometalate-based framework {[Cu(dap)<sub>2</sub>][Cu(dap)(H<sub>2</sub>O)<sub>2</sub>]<sub>2</sub>[TeMo<sub>6</sub>O<sub>24</sub>]} (<b>1</b>, dap = 1,2-diaminopropane) was synthesized and characterized by single crystal X-ray diffraction analysis, elemental analysis, IR spectroscopy, electrochemical impedance spectroscopy and powder X-ray diffraction. Complex <b>1</b> features an unusual mixed-linkage 2D metal–organic network constructed from both single [Cu(dap)<sub>2</sub>]<sup>2+</sup> and double [Cu(dap)(H<sub>2</sub>O)<sub>2</sub>]<sup>2+</sup> linkers. As a heterogeneous catalyst, <b>1</b> exhibited outstanding catalytic performance for the oxidation of 2-chloroethyl ethyl sulfide, achieving 99.1% conversion and 100% selectivity toward CEESO within 10 min at 35 °C, accompanied by excellent structural and catalytic stability. Moreover, <b>1</b> demonstrated promising electrochemical sensing properties of Cu<sup>2+</sup> ions, showing a low limit of detection of 0.492 μM, a high sensitivity of 0.426 μA μM<sup>−1</sup> and good anti-interference ability.</p></div>","PeriodicalId":803,"journal":{"name":"Transition Metal Chemistry","volume":"50 5","pages":"783 - 791"},"PeriodicalIF":1.7,"publicationDate":"2025-05-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145037182","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}
Noorhan Ali Hamza, Haider Ali Hamza, Muhsen Abood Muhsen Al-Ibadi
{"title":"Topological analysis of the electron density in the bismuth–chalcogen di- and tri-iron carbonyl complexes: [EBiFe2(CO)6]− and [EBiFe3(CO)9]− (E = Se, Te)","authors":"Noorhan Ali Hamza, Haider Ali Hamza, Muhsen Abood Muhsen Al-Ibadi","doi":"10.1007/s11243-025-00656-4","DOIUrl":"10.1007/s11243-025-00656-4","url":null,"abstract":"<div><p>DFT calculations were conducted to investigate bismuth–chalcogen di- and tri-iron carbonyl complexes: [E Bi Fen(CO)<sub>6</sub>]<sup>−</sup> (<i>E</i> = Se, Te, and <i>n</i> = 2, 3). The study employed the electron localization function and quantum theory of atoms in molecules to analyze the Fe–Fe, Fe–Se, Fe–Te, Fe–Bi, and Fe–CO bonding interactions. Additionally, a number of integral and local topological characteristics of the electron density related to these interactions were analyzed, along with the source function (SF). The topological properties and delocalization indices related to the Bi–Se and Bi–Te interactions, denoted as <i>δ</i>(Bi–E), suggest substantial direct Bi–E bonding in complexes <b>1</b> and <b>2</b>, but only a minimal Bi–E interaction in clusters <b>3</b> and <b>4</b>. The computed topological characteristics correspond well with the transition metal complexes documented in the existing literature. The topological parameters of the Fe–Fe bonds in complexes <b>1</b>–<b>4</b>, where a localized bond has been identified, differ significantly from the Fe1–Fe2 interactions in clusters <b>3</b> and <b>4</b>, where neither the bond critical point nor the bond path between the metal atoms could be identified. The SF contributions to the Fe–Fe bond critical points primarily arise from Bi atoms, which account for over 66.7%. Additionally, carbonyl O atoms contribute more than 15.7%, while E ligands contribute more than 7.6%. The topological properties and the delocalization indices associated with the Bi–Se and Bi–Te interactions, <i>δ</i>(Bi–E), imply significant direct Bi–E bonding in complexes <b>1</b> and <b>2</b>, but only a very minor Bi–E interaction in clusters <b>3</b> and <b>4</b>. The study also revealed notable <i>π</i>-back-donation from CO to Fe, as indicated by the Fe…OCO delocalization indices and SF calculations.</p></div>","PeriodicalId":803,"journal":{"name":"Transition Metal Chemistry","volume":"50 5","pages":"773 - 782"},"PeriodicalIF":1.7,"publicationDate":"2025-05-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145037202","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}