Polyhedron最新文献

{"title":"Synthesis and characterization of 1,1’-ferrocenic aryl carbonic and thiocarbonic anhydrides","authors":"Mohammad El-khateeb ,&nbsp;Matteo Cardoso ,&nbsp;Deeb Taher ,&nbsp;Frank Schaper","doi":"10.1016/j.poly.2025.117670","DOIUrl":"10.1016/j.poly.2025.117670","url":null,"abstract":"<div><div>The reactivity of 1,1′-ferrocenedicarboxylic acid (FcDA) toward aryl chloroformates and <em>O</em>-aryl chlorothioformates has been investigated to access novel ferrocene-derived (aryl carbonic) and (aryl thiocarbonic) anhydrides. The reactions of FcDA with phenyl and p-tolyl chloroformates in the presence of triethylamine afforded the corresponding bis(aryl carbonic) anhydrides, Fc(CO₂CO₂Ar)₂ [Fc = 1,1′-(C₅H₄)₂Fe; Ar = C₆H₅ (<strong>1a</strong>), p-C₆H₄CH₃ (<strong>1b</strong>)]. Similarly, treatment of FcDA with the analogous <em>O</em>-aryl chlorothioformates yielded bis(aryl thiocarbonic) anhydrides, Fc(C(<em>O</em>)SCO₂Ar)₂ [Ar = C₆H₅ (<strong>2a</strong>), p-C₆H₄CH₃ (<strong>2b</strong>)]. All compounds were characterized by UV–Vis, IR, ¹H-, and ¹³C{¹H}-NMR spectroscopy. Structural elucidation was further achieved by single-crystal X-ray diffraction, confirming the molecular architectures of the synthesized anhydrides. Density functional theory (DFT) calculations were performed at the PBE0/def2-TZVP level with CPCM solvation to further elucidate the electronic structures of the complexes. These theoretical results support the experimental UV–Vis data, offering insights into the nature of the observed electronic transitions and the frontier molecular orbitals involved.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"280 ","pages":"Article 117670"},"PeriodicalIF":2.4,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144604176","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":"Aqueous media synthesis of Ni(II) complexes of N–(p–methyl–phenethyl)–iminodiacetate(2-) chelate with or without N–heterocyclic donor ligands: Supramolecular architectures, molecular docking, Hirshfeld surfaces analysis, DFT overview and optical bandgap measurements.","authors":"D.K. Patel ,&nbsp;D. Choquesillo-Lazarte ,&nbsp;J. Niclós-Gutiérrez","doi":"10.1016/j.poly.2025.117671","DOIUrl":"10.1016/j.poly.2025.117671","url":null,"abstract":"<div><div>The stoichiometric reactions between nickel(II) hydroxy–carbonate and N–(<em>p</em>–methyl–phenethyl)–iminodiacetic acid (H₂MEpheida) in aqueous media give greenish color crystal of binary complex [Ni(MEpheida)(H₂O)₃] (<strong>1</strong>) which turns on ternary complex [Ni(MEpheida)(Him)₂(H₂O)]·2H₂O (<strong>2</strong>) on addition of imidazole (Him) ligand in the ratio of 1:1:3 for H₂MEpheida, Ni(II) salt and Him respectively. The synthesized metal complexes have been characterized by various analytical, spectroscopic viz., ¹HNMR, FTIR, UV–vis., thermogravimetry and single–crystal X–ray diffraction techniques. The crystal pattern of complex (<strong>1</strong>) differs from the related ternary complex (<strong>2</strong>) can be attributed to the ligation of N–heterocyclic ligands. The distorted octahedral geometry around the Ni(II) ion scrutinized through the single crystal X–ray analysis. As speculated, the IDA (Iminodiacetate(2-)) arm of chelate adopted <em>fac</em>–NO₂ conformation in both complexes (<strong>1</strong>) and (<strong>2</strong>). Furthermore, energy frameworks and Hirshfeld surface analysis has been utilized to scrutinized the unique intermolecular forces, specifically H–bonding interactions, 2D fingerprint plots, and supramolecular architecture. The molecular simulation processes using TD–DFT/B3LYP were employed to obtain the distinguished geometry optimizations and other related parameters viz., HOMO–LUMO, molecular electrostatic potential (MEP), frequency calculations in order to support the experimental findings. Moreover, molecular docking studies have been carried out for H₂MEpheida and their corresponding Ni(II) metal complexes (<strong>1</strong>) and (<strong>2</strong>) in the active site of CAII (PDB code: <span><span>1CNX</span><svg><path></path></svg></span>) to predict their possible interaction mode in the active site of target carbonic anhydrase II enzyme and AutoDock Vina results were further visualized and refined through receptor-ligand interactions using BIOVIA Discovery Studio 2024 program. Additionally, Tauc's equation, αhν = A(hν–E_g)r, where r = ½ for indirect and 2 for direct electronic transitions, was employed to estimate the bandgap energy (E_g) for H₂MEpheida and their corresponding Ni(II) binary and ternary complexes using UV–vis absorption data.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"280 ","pages":"Article 117671"},"PeriodicalIF":2.4,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144604764","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 chelating ring size and bite angle on the electrocatalytic water oxidation activity of copper (II) complexes","authors":"Pranjal Das ,&nbsp;Swati Basak ,&nbsp;Angarag Kashyap ,&nbsp;Kripangkar Choudhury ,&nbsp;Diganta Choudhury ,&nbsp;Apurba Kalita","doi":"10.1016/j.poly.2025.117673","DOIUrl":"10.1016/j.poly.2025.117673","url":null,"abstract":"<div><div>The electrocatalytic water oxidation activity of two mononuclear copper (II) complexes, <strong>1</strong>, [Cu(L₁)₂]²⁺, and <strong>2</strong>, [Cu(L₂)₂]²⁺, with bidentate pyridyl-amine chelating ligands <strong>L</strong>_{<strong>1</strong>}, [L₁ = (pyridin-2-yl)methanamine] and <strong>L</strong>_{<strong>2</strong>}, [L₂ = 2-(pyridin-2-yl)ethan-1-amine], has been investigated. Ligands <strong>L</strong>_{<strong>1</strong>} and <strong>L</strong>_{<strong>2</strong>} form five- and six-membered chelate rings around the copper (II) center with 81.35° and 86.55° bite angle, respectively. Complexes <strong>1</strong> and <strong>2</strong> exhibit turnover frequencies (TOF) of 5.81 s⁻¹ and 70.39 s⁻¹ at approximately 503 mV and 413 mV overpotential, respectively, in neutral phosphate buffer. Electrochemical analysis revealed that the chelate ring size and ligands bite angle has significant influence on the overall catalytic activity of these complexes.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"280 ","pages":"Article 117673"},"PeriodicalIF":2.4,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144604179","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":"A rare example of a dimeric copper(II) complex with a double nitrato κ1-O,O′;κ2-O bridge: synthesis, crystal structure, magnetic properties and Hirshfeld surface analysis","authors":"Bhargab Guhathakurta ,&nbsp;Naba Kr Mandal ,&nbsp;Prantick Shaw ,&nbsp;Samia Benmansour ,&nbsp;Carlos J. Gómez-García ,&nbsp;Jnan Prakash Naskar","doi":"10.1016/j.poly.2025.117669","DOIUrl":"10.1016/j.poly.2025.117669","url":null,"abstract":"<div><div>We present a very unusual κ¹-<em>O,O′</em>;κ²-<em>O</em> nitrate-bridged dinuclear copper(II) complex formulated as [<em>Cu</em>_<em>2</em><em>(NO</em>_<em>3</em><em>)</em>_<em>2</em><em>(L)</em>_<em>2</em>] (<strong>1</strong>), prepared with the NNO-donor Schiff base ligand, 2-(benzothiazol-2-yl-hydrazono)-1,2-diphenyl-ethanone (<strong>HL</strong>). Compound <strong>1</strong> has been characterized by elemental analysis, ESI-MS, FT-IR, UV–Vis and EPR spectroscopy. Single crystal X-ray diffraction analysis reveals that <strong>1</strong> is a Cu^II dimer with a double Cu-O-Cu bridge. It crystallizes in the monoclinic <em>P2</em>_<em>1</em><em>/n</em> space group. Solution and solid state electronic spectra confirm its identity in both phases. Magnetic susceptibility measurements of <strong>1</strong> reveal the presence of a weak antiferromagnetic Cu<img>Cu coupling through the double oxido bridge that can be fitted with a simple Bleaney-Bowers S = 1/2 dimer model with g = 2.0703(8) and J = −1.83(2) cm⁻¹. X-ray powder diffraction shows that <strong>1</strong> is obtained as a single crystalline phase. Hirshfeld surface analysis shows that intermolecular interactions in <strong>1</strong> are dominated by H<img>H, C<img>H, O<img>H and N<img>H interactions with percentages of 23.4, 15.8, 10.5 and 5.0 respectively.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"280 ","pages":"Article 117669"},"PeriodicalIF":2.4,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144604180","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":"New series of salts with 12H-quinoxalino[2,3-b]phenoxazinium cation and [Ln(hfac)4]− anions","authors":"Е.P. Ivakhnenko ,&nbsp;D.V. Korchagin ,&nbsp;N.I. Omelichkin ,&nbsp;G.V. Shilov ,&nbsp;A.A. Krainyukov ,&nbsp;M.V. Zhidkov ,&nbsp;A.I. Dmitriev ,&nbsp;O.P. Demidov ,&nbsp;P.A. Knyazev ,&nbsp;A.V. Chernyshev ,&nbsp;A.V. Palii ,&nbsp;V.I. Minkin ,&nbsp;S.M. Aldoshin","doi":"10.1016/j.poly.2025.117668","DOIUrl":"10.1016/j.poly.2025.117668","url":null,"abstract":"<div><div>The reaction of 12H-quinoxaline[2,3-<em>b</em>]phenoxazine (QOPO) with lanthanide hexafluoroacetylacetonates is accompanied by protonation of the QOPO and leads to the formation of salts of the general formula [QOPOH]⁺[Ln(hfac)₄]⁻ (Ln = Nd, Dy, Tb, Ho), whose structures have been determined by X-ray diffraction analysis and ¹H NMR spectroscopy. The compounds are characterized by long wavelength absorption and fluorescence (λ_fl = 677–740 nm). The study of the magnetic properties of the complexes has revealed that the Tb complex exhibits slow magnetic relaxation under an applied <em>dc</em> field, while the Dy complex behaves as single-ion magnet (SIM) even at zero field. These two compounds are the first examples of anionic complexes based on Dy and Tb ions coordinated by four hexafluoroacetylacetonates that exhibit the SIM properties under zero and applied <em>dc</em> fields, respectively.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"280 ","pages":"Article 117668"},"PeriodicalIF":2.4,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144595929","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":"MB-encapsulated MOF-based composites as self-calibrating sensors for selective detection of tetracycline and nitroanilines","authors":"Zhijian Xie ,&nbsp;Xue Wei ,&nbsp;Tong Zeng ,&nbsp;Jialin Li ,&nbsp;Qian Ren ,&nbsp;Yihui Wang ,&nbsp;Jiayi Liu ,&nbsp;Fengqin Wang","doi":"10.1016/j.poly.2025.117672","DOIUrl":"10.1016/j.poly.2025.117672","url":null,"abstract":"<div><div>It is well known that the introduction of dye molecules into metal-organic frameworks (MOFs) can produce self-calibrating fluorescent sensors. In this work, we successfully constructed two dual-emission composites, MB@ZnMOF1 and MB@ZnMOF2. These composites are based on ZnMOFs synthesized using the organic ligands 5-((4-carboxyphenyl)formylamino)thiophene-2-carboxylicacid (L₁) and 2,5-bis-(3,4-dicarboxyphenyl)thiopheneamide (L₂), respectively, with the luminescent dye methylene blue (MB) encapsulated within their pores. Inspired by the dual-emission properties of these MB@ZnMOFs, we investigated their potential as fluorescent sensors for antibiotic compounds and aromatic amines. The results demonstrate that MB@ZnMOFs function effectively as multi-target sensors for selective detection of tetracycline and nitroanilines, with good anti-interference capability and cyclic stability. In addition, the dual-emission peaks of the MB@ZnMOFs both exhibit pronounced fluorescence changes upon interaction with analytes, enabling them to serve as self-calibrated fluorescent probes to detect tetracycline and nitroanilines. The possible quenching mechanism can be attributed to a competitive absorption between the MB@ZnMOFs and the analytes.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"280 ","pages":"Article 117672"},"PeriodicalIF":2.4,"publicationDate":"2025-07-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144604178","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":"Two new Cr(III) complexes of pyridine-2,6-dicarboxylato(2-) ligands with pyridinium type counter cations: Synthesis, structures, thermal behavior, Hirshfeld surface analysis and antibacterial activities","authors":"Anselme E.K. Diffo ,&nbsp;Bridget N. Ndosiri ,&nbsp;Ledoux S. Pouamo ,&nbsp;Colince Nde ,&nbsp;Martin Signé ,&nbsp;Tiberiu Roman ,&nbsp;Mohammad Azam ,&nbsp;Justin Nenwa","doi":"10.1016/j.poly.2025.117667","DOIUrl":"10.1016/j.poly.2025.117667","url":null,"abstract":"<div><div>Two novel organic–inorganic hybrid salts, (C₅H₆N)[Cr(pydc)₂]·pydcH₂·5H₂O (<strong>1</strong>) and (C₅H₇N₂)[Cr(pydc)₂] (<strong>2</strong>) (C₅H₆N⁺ = pyridinium cation, C₅H₇N₂⁺ = 3-aminopyridinium cation, pydcH₂ = pyridine-2,6-dicarboxylic acid) have been synthesized and characterized using elemental analyses and spectroscopic techniques, including FT-IR and UV/Vis spectroscopic studies. Thermogravimetric analysis (TGA) was performed to evaluate the thermal stability and decomposition behavior of the synthesized compounds. The results confirmed that compound <strong>1</strong> contained water molecules, whereas compound <strong>2</strong> was determined to be anhydrous. Structural elucidation was accomplished through powder and single-crystal X-ray diffraction, enabling a detailed understanding of their crystallographic features and molecular arrangement. The [Cr(pydc)₂]⁻ anion, common to the two compounds, exhibits a six-coordinate arrangement, where the chromium(III) center adopts a distorted octahedral geometry formed by two tridentate pyridine-2,6-dicarboxylate (pydc²⁻) ligands. Compound <strong>1</strong> exhibits layers constructed of cations and complex anions, whereas compound <strong>2</strong> features alternating layers of cations and complex anions. The Hirshfeld surface analysis revealed that O⋯H/H⋯O interactions are the most abundant, with a contribution of 46.2 % (for <strong>1</strong>) and 47.8 % (for <strong>2</strong>). Evaluation of the antibacterial activity revealed that compound <strong>2</strong> exhibited high antibacterial activity against <em>E. coli</em> and <em>S. typhi</em> (MIC 0.09; 0.09 mg/mL) compared with compound <strong>1</strong> (MIC 1.17; 0.14 mg/mL) and the reference antibiotic ciprofloxacin, which showed MIC values of 0.97 mg/mL and 1.95 mg/mL, respectively.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"280 ","pages":"Article 117667"},"PeriodicalIF":2.4,"publicationDate":"2025-07-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144604177","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":"Azo-anilido complexes of ruthenium(IV) and osmium(IV): Syntheses, characterization, electronic spectra and electron transfer properties","authors":"Jahar Lal Pratihar","doi":"10.1016/j.poly.2025.117661","DOIUrl":"10.1016/j.poly.2025.117661","url":null,"abstract":"<div><div>The reaction of 2-(arylazo) aniline, (HL) [where HL is 2-(ArN<img>N)C₆H₄<img>NH₂; Ar = C₆H₅(for HL¹) and <em>p</em>-ClC₆H₄(for HL²) H represents the amino protons], with Ru(PPh₃)₃Cl₂ and (NH₄)₂OsBr₆ separately afforded the new tetravalent azo-anilido complexes Ru(L¹)₂Cl₂ (<strong>1</strong>) and Os(L²)₂Br₂ (<strong>2</strong>), respectively. Both the species Ru(L¹)₂Cl₂ (<strong>1</strong>) and Os(L²)₂Br₂ (<strong>2</strong>) were characterized by spectroscopic techniques and confirmed by x-ray structure determination. The azo-anilido chelate is six-membered; the phenyl ring adjacent to the chelate rings is distorted with four longer and two shorter bonds. This structural feature has been attributed to the delocalization of negative charge of the anionic ligands that formed in situ from the precursor (L⁻) due to dissociation of an amino proton. The ¹H NMR spectrum of (L¹)₂RuCl₂ confirms the low spin (S = 0) Ru(IV). Complexes <strong>1</strong> and <strong>2</strong> exhibited quasi-reversible reductive responses at −0.05 V, and −0.02 V respectively, vs. SCE. Both the complexes Ru(L¹)₂Cl₂ and Os(L²)₂Br₂ shows intense MLCT transitions in the visible region. The nature of the electronic spectra and electron transfer properties of both the complexes were rationalized employing DFT computation.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"279 ","pages":"Article 117661"},"PeriodicalIF":2.4,"publicationDate":"2025-07-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144587770","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":"Fabricating and applications of vanadium doped molybdenum ferrites NPs/S-g-C3N4 composites for photocatalytic degradation of dyes","authors":"Owais Ahsan ,&nbsp;Hira Ehsan ,&nbsp;Fatima Tahir ,&nbsp;Sohail Nadeem ,&nbsp;Mobeen Murtaza ,&nbsp;Muhammad Shahzad Kmal ,&nbsp;Muhammad Azeem Akbar Rana ,&nbsp;Hafiza Tanawish Habib ,&nbsp;Ali Bahadur ,&nbsp;Shahid Iqbal ,&nbsp;Sajid Mahmood ,&nbsp;Syed Kashif Ali ,&nbsp;Shaimaa A.M. Abdelmohsen ,&nbsp;Randa A. Althobiti","doi":"10.1016/j.poly.2025.117662","DOIUrl":"10.1016/j.poly.2025.117662","url":null,"abstract":"<div><div>This investigation looks at the way sulfur-doped graphitic carbon nitride (S-g-C₃N₄) and vanadium-doped iron molybdate (<em>V</em>-MoFe₂O₄) nanocomposites are prepared and tested for their effect on environmental protection. To produce S-g-C₃N₄, a solvothermal method was used and <em>V</em>-MoFe₂O₄ nanoparticles were made using a hydrothermal approach by doping vanadium at differing amounts (2, 4, 6, 8 and 10 mol%). The methylene blue (MB) dye was tested under sunlight to evaluate photocatalytic activity. <em>V</em>-MoFe₂O₄ with an 8 mol% amount of V achieved the maximum degradation efficiency in all the samples. Nanocomposites with certain contents of S-g-C₃N₄ (including 10 %, 50 %, 70 % and 90 %) and 8 % of V-MoFe₂O₄ formulations were made to increase activity. The S-g-C₃N₄/<em>V</em>-MoFe₂O₄ composite (90 % S-g-C₃N₄ + 8 % V-MoFe₂O₄) did the best job of removing dyes in a little over two hours. Through X-ray diffraction (XRD), FTIR, scanning electron microscopy (SEM) and U<em>V</em>–visible spectroscopy, we showed that the nanocomposites formed correctly and had good structural features. According to these findings, the S-g-C₃N₄/V-MoFe₂O₄ combination could be a good choice for treating wastewater using solar power.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"279 ","pages":"Article 117662"},"PeriodicalIF":2.4,"publicationDate":"2025-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144571951","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":"On the anomalous enthalpies of formation of chloro- and bromomethylidynetricobalt enneacarbonyl, ClC[CO(CO)3]3 and BrC[CO(CO)3]3: Computational, thermochemical and quantum chemistry provide understanding","authors":"Maja Ponikvar-Svet ,&nbsp;Kathleen Frances Edwards ,&nbsp;Joel Fredric Liebman","doi":"10.1016/j.poly.2025.117666","DOIUrl":"10.1016/j.poly.2025.117666","url":null,"abstract":"<div><div>Chloro- and bromomethylidynetricobalt enneacarbonyl, ClC[Co(CO)₃]₃, and BrC[Co(CO)₃]₃, respectively, may be recognized as archetypal functionalized heteronuclear clusters, as polyhedral metal carbonyls derivatives. However, their reported enthalpies of formation and sublimation are inconsistent with those from other thermochemical studies. Using analogies from literature on organic, inorganic and organometallic chemistry, and contemporary quantum chemical calculations, new values are suggested for consistency in chemical understanding.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"279 ","pages":"Article 117666"},"PeriodicalIF":2.4,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144572411","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}