Journal of Organometallic Chemistry最新文献

{"title":"Second sphere control of CO2 reduction selectivity by iron porphyrins: The role of spin state","authors":"Suman Patra ,&nbsp;Soumili Ghosh ,&nbsp;Soumya Samanta,&nbsp;Abhijit Nayek,&nbsp;Abhishek Dey","doi":"10.1016/j.jorganchem.2024.123439","DOIUrl":"10.1016/j.jorganchem.2024.123439","url":null,"abstract":"<div><div>Iron porphyrins are reported to reduce CO₂ selectively to CO. Hydrogen bonding interactions are reported to facilitate this 2e⁻/2H⁺ reduction process. A series of iron porphyrins are reported here where hydrogen bonding distal super structure is introduced systematically. The results show that the selectivity for 2e⁻/2H⁺ CO₂ reduction changes dramatically from CO to HCOOH as hydrogen bonding interactions are introduced. The resonance Raman data of the Fe(II)-COOH intermediate, trapped at −80^oC, show that the spin state of this species changes from low spin to high spin as hydrogen bonding is introduced. The spin state of the Fe(II)-COOH intermediate seems to determine the selectivity of 2e⁻/2H⁺ CO₂ reduction in iron porphyrins.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1023 ","pages":"Article 123439"},"PeriodicalIF":2.1,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142652594","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":"Low-intensity-visible-light-driven photocatalytic CO2 reduction by rhenium tricarbonyl complexes based on pyridyl-triazole ligands","authors":"Phuong N. Nguyen ,&nbsp;Hoai Phuong Pham ,&nbsp;Quang V. Dang ,&nbsp;Khanh D. Pham ,&nbsp;Giang N. Doan ,&nbsp;Thi H. Ho ,&nbsp;Tuan M. Nguyen ,&nbsp;N. Nguyen Dang","doi":"10.1016/j.jorganchem.2024.123438","DOIUrl":"10.1016/j.jorganchem.2024.123438","url":null,"abstract":"<div><div>Photocatalytic CO₂ reduction (PCO2R) based on [Re(pyridyl-triazole)(CO)₃Cl] is demonstrated in various media, using triethanolamine (TEOA) and water as electron donors (EDs) under low-intensity visible-light irradiation. Three complexes exhibited PCO2R activity with high CO selectivity (&gt; 91%) in DMF-TEOA (DMF: N, N’-dimethylformamide), CH₃CN-TEOA (CH₃CN: acetonitrile), and DMF-H₂O mixed solvents. Among these, the DMF-TEOA mixed solvents showed the highest efficiency and CO selectivity in photocatalytic CO₂ reduction to CO. Re(Hph) and Re(dcbpy) demonstrated photocatalytic activity even under low-intensity irradiation in DMF-H₂O, indicating their potential contribution to the development of artificial photosynthetic materials.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1023 ","pages":"Article 123438"},"PeriodicalIF":2.1,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142652651","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":"Sidearm modified phosphine ligands for Rh complex-catalyzed hydroformylation: Mechanistic pathway and structure-activity relationship","authors":"Jie Ding ,&nbsp;Zidi Miao ,&nbsp;Maoshuai Li,&nbsp;Qi Yang,&nbsp;Yi Feng,&nbsp;Mei-Yan Wang,&nbsp;Xinbin Ma","doi":"10.1016/j.jorganchem.2024.123436","DOIUrl":"10.1016/j.jorganchem.2024.123436","url":null,"abstract":"<div><div>Development of high-performance phosphine ligands is an effectual strategy to improve the homogeneous hydroformylation reaction. This study designed a series of amide/ester sidearms-modified phosphine ligands with different characteristics (e.g., proton affinity, steric hindrance) for homogeneous Rh-complex in hydroformylation of formaldehyde. The sidearms-modified ligands with the stronger proton affinity serve to transfer proton from the hydrido rhodium species to the activated formaldehyde via the sidearms to generate the critical hydroxymethyl rhodium species that favours the hydroformylation to glycolaldehyde, yielding significantly improved reaction rates (twice as much as PPh₃). The bulky sidearm with larger steric hindrance can stretch the hydrogen bond between the product and the sidearm, suppressing the by-product production and improving the target selectivity. A potential reaction mechanism involving sidearm-induced deprotonation and inner-molecule proton transfer was proposed for the sidearm-modified phosphine ligands coordinated Rh complex based on the DFT calculation and experimental study. This study can trigger the innovative phosphine ligand design with special functional sidearms for hydroformylation.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1023 ","pages":"Article 123436"},"PeriodicalIF":2.1,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142652650","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 and catalytic application to form cyclic carbonates of novel Pd(II) Cu(II), and Fe(II) benzoate-based Schiff base metal complexes","authors":"Hatice Gamze Sogukomerogullari ,&nbsp;Emine Aytar ,&nbsp;Reşit Çakmak ,&nbsp;Eyüp Başaran","doi":"10.1016/j.jorganchem.2024.123424","DOIUrl":"10.1016/j.jorganchem.2024.123424","url":null,"abstract":"<div><div>This work describes the synthesis and characterisation of six novel Schiff base complexes, Cu(II), Pd(II), and Fe(II), which, under the right circumstances, function as very efficient catalysts for the production of cyclic carbonates from CO₂ and epoxides. FT-IR spectroscopy, elemental analysis, UV–Vis spectroscopy, molar conductivity, melting point, and magnetic susceptibility measurements are among the spectroscopic methods used to characterize newly synthesized complexes. The molar conductivity values, ranging from 2.58 to 4.03 µS/cm, suggest that the complexes exhibit no molar conductivity. Co-catalysts, such as 4-(dimethylamino)pyridine, pyridine, triethylamine, and triphenyl phosphine, were used in these processes, both with and without one. 4-(Dimethylamino)pyridine was used as the co-catalyst in the catalytic studies. Additionally, a number of variables that affect the cycloaddition process were examined, including the temperature, CO₂ pressure, reaction time, and co-catalyst. All novel catalysts exhibited exceptional catalytic activity and selectivity in the catalytic assays. Regarding the coupling of CO₂ and epichlorohydrin as epoxides, the L2-Cu catalyst outperformed other catalysts in terms of catalytic activity (90.7%) and selectivity (98.9%).</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1023 ","pages":"Article 123424"},"PeriodicalIF":2.1,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142571513","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":"Hybridizing engineering strategy of decatungstate III: Transition metal modified carbon quantum dot-regulated photo-catalytic oxidation performance of decatungstate","authors":"Anqun Su ,&nbsp;Dabo Jiang ,&nbsp;Wenwei Hu ,&nbsp;Shuting Liang ,&nbsp;Kai Yu ,&nbsp;Weijie Zhou ,&nbsp;Jing Wang ,&nbsp;Zaihui Fu ,&nbsp;Yachun Liu ,&nbsp;Jianxin Liu","doi":"10.1016/j.jorganchem.2024.123432","DOIUrl":"10.1016/j.jorganchem.2024.123432","url":null,"abstract":"<div><div>The selective oxidation of hydrocarbons (RH) by dioxygen (O₂) is a very important method for industrial production of bulk oxygen-containing compounds, However, due to the high chemical inertness of RH and O₂, achieving this reaction under mild conditions still faces significant challenges. This paper discloses an efficient hybridizing engineering (HE) strategy of decatungstate (DT) with 3d transition metal ions (Mⁿ⁺=Ni²⁺, Co²⁺ or Cu²⁺)-modified carbon quantum dots (Mⁿ⁺/CQD) as the dopants. Compared to pure CQD, The Mⁿ⁺/CQD can more efficiently combine with DT anion to fabricate a high-quality hybrid <em>via</em> electrostatic interactions, thereby bestowing the hybrid with an enhanced visible light response especially the separation efficiency of photo-generated charge pairs. Furthermore, the above hybridization effects of Mⁿ⁺/CQD on DT anion can be fine-tuned and gradually improved with a change of the metal ion from Cu²⁺, Co²⁺ to Ni²⁺, along with a continuous enhancement of the hybrid's photo-catalytic efficiency in the visible light- triggered selective oxidation of ethylbenzene with O₂ in acetonitrile. The best Ni²⁺/CQD-doped TBADT can achieve ca. 48% ethylbenzene conversion and 87.6% acetophenone selectivity in the presence of 2 M HCl, and it also shows a much higher photo-catalytic activity for the photo-oxidation of toluene, cyclohexane and benzyl alcohol compared to pure TBADT. The HE strategy with Mⁿ⁺/CQD as the cationized hybridizers is much superior to that with pure CQD or Ni²⁺ as the hybridizer in hoisting the photo-catalytic performance of DT.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1023 ","pages":"Article 123432"},"PeriodicalIF":2.1,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142593978","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":"C3-symmetric triarylboron building blocks: Synthesis, structures, and photophysical properties","authors":"Vishal Singh,&nbsp;Ramaswamy Murugavel","doi":"10.1016/j.jorganchem.2024.123412","DOIUrl":"10.1016/j.jorganchem.2024.123412","url":null,"abstract":"<div><div>Synthesis of C₃-symmetric triarylboranes, tris(4-bromo-2,6-dimethylphenyl)-borane <strong>(1)</strong>, N,N',N''-(boranetriyltris(3,5-diisopropyl-3′,5′-dimethyl-[1,1′-biphenyl]-4′,4-diyl))tris(1,1-diphenylmethanimine) (<strong>2</strong>), N,N',N''-(boranetriyltris(3′,5′-dimethyl-[1,1′-biphenyl]-4′,4-diyl))tris-(1,1-diphenylmethanimine) (<strong>3</strong>), 4′,4′'',4′''''-boranetriyltris(3′,5′-dimethyl-[1,1′-biphenyl]-4-carbaldehyde) (<strong>4),</strong> 4,4′,4′'-boranetriyltris(3,5-dimethylaniline) (<strong>5</strong>), 4′,4′'',4′''''-borane-triyltris(3′,5′-dimethyl-[1,1′-biphenyl]-4-carbonitrile) (<strong>6</strong>), 4′,4′'',4′''''-boranetriyltris(3′,5′-dimethyl-[1,1′-biphenyl]-4-amine) (<strong>7</strong>), and 4,4′,4′'-boranetriyltris(3,5-dimethylbenzaldehyde) (<strong>8</strong>) has been accomplished using well-known synthetic methodologies. These new potential building blocks have been characterized by various spectroscopic and analytical techniques and their photophysical properties have been examined. It is observed that photophysical properties of these compounds are enhanced with π conjugation expansions along the branches when donor moieties such as -NH₂ groups are present at the para-position of the aryl rings. The highest quantum yield of 0.293 is observed for 4′,4′'',4′''''-boranetriyltris(3′,5′-dimethyl-[1,1′-biphenyl]-4-amine) (<strong>7</strong>). Interestingly, red-shifted fluorescence spectra follow the same trend as absorption spectra. The fluorescence lifetime increases with the number of donor moieties. The present findings demonstrate the possible use of these C₃-symmetric boron-containing building blocks in developing new polymeric materials with improved photophysical properties for various applications.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1022 ","pages":"Article 123412"},"PeriodicalIF":2.1,"publicationDate":"2024-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142538524","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":"Substituent and metal effects on CC σ-complex stabilization","authors":"Yumeng Cao,&nbsp;Dean J. Tantillo","doi":"10.1016/j.jorganchem.2024.123414","DOIUrl":"10.1016/j.jorganchem.2024.123414","url":null,"abstract":"<div><div>Three-center, two-electron bonding arrays in σ-complexes between C<img>C bonds and transition metals were examined using density functional theory computations. Variations in ligands and metals were connected to variations in strengths of bonding interactions in these arrays.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1023 ","pages":"Article 123414"},"PeriodicalIF":2.1,"publicationDate":"2024-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142560664","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":"Supported Au NPs over magnetic chitosan-gelatin nanocomposite: Investigation of its catalytic activity for one-pot synthesis of tetrazoles, study of antioxidant activity and anti-uterine cancer performances","authors":"Qian Qiu ,&nbsp;JianRong Song ,&nbsp;Hui Zheng ,&nbsp;Marjan Shahriari ,&nbsp;Attalla F. El-kott ,&nbsp;Ali G. Alkhathami ,&nbsp;Kareem Morsy","doi":"10.1016/j.jorganchem.2024.123423","DOIUrl":"10.1016/j.jorganchem.2024.123423","url":null,"abstract":"<div><div>This paper reports the synthesis of a novel class of Fe₃O₄@CS-Gl/Au core-shell pattern nanoparticles by employing Au NPs and chitosan-gelatin composite. The biogenic synthesis was mediated by dual composite hydrogel of chitosan and gelatin as a green reducing as well as stabilizing agent under ambient conditions. Physicochemical features the so obtained nanomaterial was assessed by using FT-IR, TEM, FE-SEM, EDX, elemental mapping, VSM and XRD. Click synthesis of 5-substituted-1H-tetrazoles utilizing aryl halides was our aim in catalytic investigation. The Fe₃O₄@CS-Gl/Au catalyst, which is highly effective and reusable, was used to catalyze the [3 + 2]-cycloaddition of benzonitriles with NaN₃, leading to the solvent-free synthesis of corresponding tetrazole derivatives at 120 °C. This method was carried out using K₄[Fe(CN)₆] as a non-hazardous cyanide precursor. Following a 12-hour process, the different substrates produced yields ranging from 70 to 96 %. Hot filtration, leaching and reusability studies were conducted 12 times in a succession, all of which confirmed the catalyst's resilience. Furthermore, in the biological studies % cell viability of Fe₃O₄@CS-Gl/Au NPs was found very low against common human uterine cell lines i.e. AN3-CA and HEC-1-A, devoid of any cytotoxicity on normal cell lines like HUVEC. The best anti-uterine effect was observed against the AN3-CA cell line. For investigating the antioxidant properties of nanobio-composite, the DPPH assay was used. Fe₃O₄@CS-Gl/Au NPs inhibited half of the DPPH molecules in the concentration of 139 µg/mL. The antioxidant activity of the NPs is significantly related to its anti-uterine cancer potentials. Based on the above findings, the Fe₃O₄@CS-Gl/Au NPs could be administered in restricting diverse human cancers.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1023 ","pages":"Article 123423"},"PeriodicalIF":2.1,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142554767","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":"Expeditious and selective synthesis of 2,4,5-trialkyl-1H-imdazoles and benzimidazoles via multicomponent one-pot reaction catalyzed by Schiff base dioxomolybdenum(VI) complex","authors":"Jiaxin Zhang ,&nbsp;Miao Wang ,&nbsp;Jun Zhang ,&nbsp;Qingyi Zhang ,&nbsp;Lin Sun ,&nbsp;Taiping Gao ,&nbsp;Weili Wang ,&nbsp;Tomás Guerrero ,&nbsp;Xiuwei Gao","doi":"10.1016/j.jorganchem.2024.123420","DOIUrl":"10.1016/j.jorganchem.2024.123420","url":null,"abstract":"<div><div>Imidazoles and benzimidazoles are privileged heterocyclic compounds that can be extensively found in medicinal and materials chemistry, however, the experimental procedures for their synthesis are limited to multicomponent condensation reactions and normally are strongly dependent upon the desired substitution pattern, consequently several procedures with different conditions and catalysts are available in literature. Accordingly, the development of synthetic methodologies to afford these compounds remains a very attractive research problem. In this regard, dioxomolybdenum based catalysts are emerging as versatile and non-expensive reagents for a myriad of chemically relevant transformations. Within this context, an expedient and efficient synthesis of 2,4,5-trialkyl-1<em>H</em>-imidazoles and benzimidazoles from a multicomponent one-pot condensation has been developed with a tridentate Schiff base dioxomolybdenum(VI) complex, resulting in an efficient, simple and readily available catalyst to promote the aforementioned reaction. This reaction offers advantages such as good to excellent yields, good selectivity of products, low catalyst loadings and simple reaction work-up.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1023 ","pages":"Article 123420"},"PeriodicalIF":2.1,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142593980","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":"Advanced-designed Ru(II) complexes containing phosphinite ligands derived from chiral amino alcohols: Electrochemical behavior, DFT calculations, and biological activity","authors":"Nermin Meriç ,&nbsp;Uğur Işık ,&nbsp;Anuar Dauletbakov ,&nbsp;Darya Zolotareva ,&nbsp;Alexey Zazybin ,&nbsp;Mehmet Şerif Sever ,&nbsp;Veysi Okumuş ,&nbsp;Nil Ertekin Binbay ,&nbsp;Veysel Binbay ,&nbsp;Cezmi Kayan ,&nbsp;Remziye Güzel ,&nbsp;Murat Aydemir","doi":"10.1016/j.jorganchem.2024.123410","DOIUrl":"10.1016/j.jorganchem.2024.123410","url":null,"abstract":"<div><div>We report two phosphinite ligands derived from chiral amino alcohols, and their complexes with ruthenium(II). These compounds were characterized by spectroscopic methods. Then, antimicrobial, antioxidant, and DNA binding activities of the chiral Ru(II)-phosphinite complexes were tested. Complex (1<em>R</em>)-2-{benzyl[(1<em>S</em>)-1-(naphthalen-1-yl)ethyl]amino}-1-phenylethyl diphenylphos- phinito[dichloro(η⁶-<em>p</em>-cymene)ruthenium(II)], 7 showed both the highest radical scavenging activity (90.93 ± 0.98 %) and the highest metal chelating activity (65.45 ± 1.46 %) at 200.0 mg l^-1 concentration. In addition, all of complexes had different rates of binding activity to calf thymus DNA (CT-DNA). Moreover, extensive theoretical and experimental investigations were conducted to gain a more profound understanding of the chemical descriptors and the diverse electronic transitions taking place within the ruthenium complexes, as well as their electrochemical characteristics.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1023 ","pages":"Article 123410"},"PeriodicalIF":2.1,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142525789","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}