Journal of Organometallic Chemistry最新文献

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Copper catalysed construction of C-P bond: C-H functionalization
IF 2.1 3区 化学
Journal of Organometallic Chemistry Pub Date : 2025-01-12 DOI: 10.1016/j.jorganchem.2025.123512
Rajnikant N. Ghoghari, Kishor H. Chikhalia
{"title":"Copper catalysed construction of C-P bond: C-H functionalization","authors":"Rajnikant N. Ghoghari,&nbsp;Kishor H. Chikhalia","doi":"10.1016/j.jorganchem.2025.123512","DOIUrl":"10.1016/j.jorganchem.2025.123512","url":null,"abstract":"<div><div>Over the past decades, transition metal catalysed synthesis of organophosphorus compounds appears with rapid advancements. Phosphorus annulated compounds achieved popularity because of their broad range of applications such as, ligands in catalysis, as bioactive natural products, medicines, agrochemicals and building blocks. It leads to further augmentation of relevant methodologies for the construction of bioactive scaffolds having C-P bond, which is new frontier in synthetic organic chemistry. Currently, organophosphorus compounds are being synthesised through transition metal catalyst. Metal catalysed pre-functionalization of heterocycles through phosphorus hydrogen (P- H) bond leads to the C-P linked heterocycles through C<img>-H functionalization concept. The synthesis of several structurally varied complex compounds requires the use of copper catalysed reactions because of their strong bond forming abilities under moderate reaction conditions and broad functional group tolerance.</div><div>This review (2015–2024) focusses the advancement in copper catalysed C-P bond formation encompassing both intra and intermolecular transformations. Key aspects like reaction mechanism, substrate scope, catalyst design are discussed highlighting the versatility and applicability of synthetic approach. Furthermore, applications of the synthetic routes in the design of building blocks, agrochemicals and functional materials have been emphasized with respective mechanisms. Finally challenges and future directions in this field are outlined, aiming inspiration to researchers involved in construction of C-P bond.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1027 ","pages":"Article 123512"},"PeriodicalIF":2.1,"publicationDate":"2025-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143333167","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}
引用次数: 0
Synthesis and characterization of gold(I) N-heterocyclic carbenes complexes bearing methacrylate moiety
IF 2.1 3区 化学
Journal of Organometallic Chemistry Pub Date : 2025-01-11 DOI: 10.1016/j.jorganchem.2025.123514
Rim Hamdi , Ida Staccioni , Julie Gerber , Sandrine Rup-Jacques , Jasmine Hertzog , Vincent Carré , Michèle Sindt , Corentin Lefebvre , Taoufik Boubaker , Jean-François Longevial
{"title":"Synthesis and characterization of gold(I) N-heterocyclic carbenes complexes bearing methacrylate moiety","authors":"Rim Hamdi ,&nbsp;Ida Staccioni ,&nbsp;Julie Gerber ,&nbsp;Sandrine Rup-Jacques ,&nbsp;Jasmine Hertzog ,&nbsp;Vincent Carré ,&nbsp;Michèle Sindt ,&nbsp;Corentin Lefebvre ,&nbsp;Taoufik Boubaker ,&nbsp;Jean-François Longevial","doi":"10.1016/j.jorganchem.2025.123514","DOIUrl":"10.1016/j.jorganchem.2025.123514","url":null,"abstract":"<div><div>The study focuses on gold(I) N-heterocyclic carbene (NHC) complexes. The research aims to synthesize a family of four mono- and four bis-gold(I) N-heterocyclic carbene complexes, each bearing a methacrylate motif, with yields ranging from 63% to 98%. Two model complexes from this series were tested toward sulfur-based nucleophilic attack to assess the possibility of a Michael addition to the acrylate motif, with a view to future bioconjugation. Experimental results reveal that thiolate addition occurs exclusively at the gold(I) center, regardless of whether the N-heterocyclic carbene is a mono- or a bis-carbene, leaving the acrylate motif untouched. This outcome is supported by theoretical calculations, which predict an activation energy of at least 4 kcal/mol favoring nucleophilic attack at the gold(I) center. These findings suggest that gold(I) NHC complexes could serve as effective \"clickable\" motifs in themselves, challenging the necessity of further functionalizing them with additional clickable groups for bioconjugation applications.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1027 ","pages":"Article 123514"},"PeriodicalIF":2.1,"publicationDate":"2025-01-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143332195","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}
引用次数: 0
Isolation and characterization of [n-Bu2Sn(OH2)(phen)(OSO2CF3)](O3SCF3) (phen = 1,10-phenanthroline): The missing link
IF 2.1 3区 化学
Journal of Organometallic Chemistry Pub Date : 2025-01-10 DOI: 10.1016/j.jorganchem.2025.123511
Hélène Cattey, Marie-José Penouilh, Quentin Bonin, Laurent Plasseraud
{"title":"Isolation and characterization of [n-Bu2Sn(OH2)(phen)(OSO2CF3)](O3SCF3) (phen = 1,10-phenanthroline): The missing link","authors":"Hélène Cattey,&nbsp;Marie-José Penouilh,&nbsp;Quentin Bonin,&nbsp;Laurent Plasseraud","doi":"10.1016/j.jorganchem.2025.123511","DOIUrl":"10.1016/j.jorganchem.2025.123511","url":null,"abstract":"<div><div>Reaction of [<em>n</em>-Bu<sub>2</sub>Sn(<em>μ</em>-OH)(H<sub>2</sub>O)(OSO<sub>2</sub>CF<sub>3</sub>)]<sub>2</sub> (<strong>1</strong>) with 1,10-phenanthroline (phen) in acetonitrile at room temperature in a 1:0.75 molar ratio leads to the formation of a mixture of three species comprising [{<em>n</em>-Bu<sub>2</sub>Sn(H<sub>2</sub>O)}<sub>2</sub>O·<em>n</em>-Bu<sub>2</sub>Sn(OH)<sub>2</sub>](O<sub>3</sub>SCF<sub>3</sub>)<sub>2</sub> (<strong>2</strong>) and [{<em>n</em>-Bu<sub>2</sub>Sn(OH)(OSO<sub>2</sub>CF<sub>3</sub>)}(<em>n</em>-Bu<sub>2</sub>SnO)]<sub>2</sub> (<strong>3</strong>) as well as the title compound [<em>n</em>-Bu<sub>2</sub>Sn(OH<sub>2</sub>)(phen)(OSO<sub>2</sub>CF<sub>3</sub>)](O<sub>3</sub>SCF<sub>3</sub>) (<strong>4</strong>). Compounds <strong>1, 2</strong> and <strong>3</strong> crystallize in dichloromethane at –20 °C, while <strong>4</strong> remains in solution under these conditions. After filtration and by repeating this procedure several times (four in total), it was possible to isolate only <strong>4</strong>. Single-crystals of <strong>4</strong>, suitable for an X-ray diffraction analysis, were grown from a mixture of dichloromethane/toluene. Compound <strong>4</strong> consists of a mononcationic di-<em>n</em>-butyltin(IV) complex, <em>N,N</em>-chelated by one phen ligand and coordinated by one water molecule and one trifluoromethanesulfonato ligand. In the crystal lattice, the individual molecule of <strong>4</strong> are associated in dimers resulting from intermolecular hydrogen-bonding interactions between aqua ligands and trifluoromethasulfonate counteranions. The isolation and characterization of compound <strong>4</strong> provides new insights into the reactivity of <strong>1</strong> with phen.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1027 ","pages":"Article 123511"},"PeriodicalIF":2.1,"publicationDate":"2025-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143332193","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Cu-catalyzed reductive Friedel-Crafts alkylation of indoles with ketones for one-pot synthesis of 3-substituted indoles
IF 2.1 3区 化学
Journal of Organometallic Chemistry Pub Date : 2025-01-09 DOI: 10.1016/j.jorganchem.2025.123513
Wengang Wang, Zewei Mao
{"title":"Cu-catalyzed reductive Friedel-Crafts alkylation of indoles with ketones for one-pot synthesis of 3-substituted indoles","authors":"Wengang Wang,&nbsp;Zewei Mao","doi":"10.1016/j.jorganchem.2025.123513","DOIUrl":"10.1016/j.jorganchem.2025.123513","url":null,"abstract":"<div><div>3-Substituted indoles have attracted more and more attention bearing good bioactivity. In this work, we have explored an effective method for Cu-catalyzed reductive Friedel-Crafts alkylation of indoles with ketones using Et<sub>3</sub>SiH as reductant to give 3-substituted indoles in good yields, and it could be applicable for both substituted indoles and N-methylindoles.</div><div>2024 Elsevier Ltd. All rights reserved.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1027 ","pages":"Article 123513"},"PeriodicalIF":2.1,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143332194","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}
引用次数: 0
Facile synthesis and spectral analysis of the bioactive spiroborate compounds as a novel therapeutic agent for computational insights, biological evaluation, and applications
IF 2.1 3区 化学
Journal of Organometallic Chemistry Pub Date : 2025-01-09 DOI: 10.1016/j.jorganchem.2025.123510
Metin Yildirim , Eyyup Yasar , Adem Necip , Mehmet Cimentepe , Burcu Demirbağ , Ahmet Kilic
{"title":"Facile synthesis and spectral analysis of the bioactive spiroborate compounds as a novel therapeutic agent for computational insights, biological evaluation, and applications","authors":"Metin Yildirim ,&nbsp;Eyyup Yasar ,&nbsp;Adem Necip ,&nbsp;Mehmet Cimentepe ,&nbsp;Burcu Demirbağ ,&nbsp;Ahmet Kilic","doi":"10.1016/j.jorganchem.2025.123510","DOIUrl":"10.1016/j.jorganchem.2025.123510","url":null,"abstract":"<div><div>Boron-containing compounds (BCCs) have emerged as a new class of organic molecules in pharmaceutical chemistry as novel drug candidates for extensive therapeutic applications. In this context, the five novel bioactive spiroborate compounds <strong>(S<sub>1</sub>-S<sub>5</sub>)</strong> were synthesized by condensation reaction of Schiff base ligands <strong>(L<sub>1</sub>-L<sub>5</sub>)</strong>, 1,3-dioxane-5,5-dimethanol, and boric acid with high yields. The bioactive spiroborate compounds <strong>(S<sub>1</sub>-S<sub>5</sub>)</strong> were characterized by NMR (<sup>1</sup>H and <sup>11</sup>B) spectra, FT-IR spectra, UV–Vis spectra, LC-MS/MS spectrometry, elemental analysis, and melting point measurement techniques. The anti-cancer activity in A549 lung cancer cells and inhibitory effects of α-glucosidase with acetylcholinesterase (AChE) enzymes of the synthesized spiroborate compounds were investigated. In addition, the anti-bacterial activity of spiroborate compounds against <em>Staphylococcus aureus, Enterococcus faecalis, Pseudomonas aeruginosa,</em> and <em>Escherichia coli</em> were investigated, respectively. On the other hand, anti-biofilm activity against <em>Pseudomonas aeruginosa</em> was assessed. <em>In silico</em> studies were also conducted on the synthesized spiroborate molecules <strong>(S<sub>1</sub>-S<sub>5</sub>)</strong>. Among the synthesized spiroborate compounds, spiroborate <strong>(B<sub>5</sub>)</strong> was identified as the most potent anticancer agent with an IC<sub>50</sub> of 352.5 µg/ml, in contrast spiroborate <strong>(B<sub>3</sub>)</strong> exhibited the strongest α-glucosidase inhibition (68 %) and anti-bacterial activity. Furthermore, spiroborate <strong>(B<sub>4</sub>)</strong> was the most effective AChE inhibitor (61 %). Besides, spiroborate <strong>(B<sub>4</sub>)</strong> exhibited strong antibacterial activity against <em>S. aureus</em> and <em>E. coli</em> with MIC values of 7.81 μg/mL. Spiroborate compounds <strong>(S<sub>1</sub>-S<sub>5</sub>)</strong> exhibited significant dose-dependent biofilm inhibitory activity against <em>P. aeruginosa</em>. The binding affinities of spiroborate <strong>(B<sub>4</sub>)</strong> to the proteins 3VSL and 4WUB were calculated as −4.16 and −4.26 kcal/mol.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1027 ","pages":"Article 123510"},"PeriodicalIF":2.1,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143332389","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}
引用次数: 0
The recent advances of copper(II)-β-cyclodextrin complex as a practical catalyst system for various organic conversions: A review
IF 2.1 3区 化学
Journal of Organometallic Chemistry Pub Date : 2025-01-09 DOI: 10.1016/j.jorganchem.2025.123509
Sara Payamifar , Majid Abdouss , Ahmad Poursattar Marjani
{"title":"The recent advances of copper(II)-β-cyclodextrin complex as a practical catalyst system for various organic conversions: A review","authors":"Sara Payamifar ,&nbsp;Majid Abdouss ,&nbsp;Ahmad Poursattar Marjani","doi":"10.1016/j.jorganchem.2025.123509","DOIUrl":"10.1016/j.jorganchem.2025.123509","url":null,"abstract":"<div><div>Nowadays, a considerable amount of research is focused on cyclodextrin chemistry because it is economically and environmentally helpful; also, they are eco-friendly biomimetic materials, water-soluble, low-price, commercially available, easily functionalized, and non-toxic. These particular properties make cyclodextrin (CD) an appealing and invaluable field for study. β-CD can make host-guest complexes by non-covalent bonding, leading to highly selectively catalyzed chemical reactions. Indeed, β-CD has been vastly applied as a green nanocatalyst for organic conversions. In this regard, Cu(II)-β-CD is a dinuclear complex with great stability constants that recently received massive attention in organic chemistry. Cu(II)-β-CD is easily accessible and structurally simple and can be a promising catalyst in different organic conversions. This review concentrates on using copper(II)-β-CD catalyst as an advantageous catalyst in the diverse organic reactions and summary articles.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1027 ","pages":"Article 123509"},"PeriodicalIF":2.1,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143333168","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}
引用次数: 0
Advancing chemistry sustainably: From synthesis to benefits and applications of green synthesis
IF 2.1 3区 化学
Journal of Organometallic Chemistry Pub Date : 2025-01-06 DOI: 10.1016/j.jorganchem.2025.123508
Arwa sultan Alqahtani , Shehab Elbeltagi
{"title":"Advancing chemistry sustainably: From synthesis to benefits and applications of green synthesis","authors":"Arwa sultan Alqahtani ,&nbsp;Shehab Elbeltagi","doi":"10.1016/j.jorganchem.2025.123508","DOIUrl":"10.1016/j.jorganchem.2025.123508","url":null,"abstract":"<div><div>Green synthesis is a method of chemical synthesis that aims to reduce the environmental impact of chemical reactions and techniques. Green synthesis techniques use plant extracts, microorganisms, or proteins as bio-capping and bio-decreasing agents and their role as bio-nanofactories for prepare biogenic nanoparticles (NPs). Green chemistry emphasizes the minimization of hazardous compounds, reduction of waste generated in conventional organic synthesis, and consideration of both production and disposal impacts. Since 2011, the adoption of green chemistry techniques has led to a 27 % reduction in chemical waste, with enhanced chemical recycling playing a significant role. Key reduction strategies include process modifications, elimination of toxic reagents, and reduction in the number of steps required in organic synthesis. Moreover, green chemistry-based sustainable synthesis and nanomaterial surface fabrication have attracted attention due to their superior catalytic properties, ease of handling, reusability, cost-effectiveness, and biocompatibility. For instance, metal NPs synthesized from plant extracts and animal waste have gained popularity as bio-reductants for various organic transformations. The pharmaceutical industry is increasingly committed to sustainable chemistry practices to produce modern medicines and improve the greenness of numerous drugs. This review will primarily examine the steps, concepts, and techniques fundamental to green chemistry.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1027 ","pages":"Article 123508"},"PeriodicalIF":2.1,"publicationDate":"2025-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143333166","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}
引用次数: 0
Rh-catalyzed (4+1) carbocyclization of chalcones with internal alkynes: A DFT study
IF 2.1 3区 化学
Journal of Organometallic Chemistry Pub Date : 2025-01-03 DOI: 10.1016/j.jorganchem.2025.123507
Xueli Mu , Yihang Zhou , Huaishen Li , Jing Zhang , Jian Zhang , Kang Lv , Tao Liu
{"title":"Rh-catalyzed (4+1) carbocyclization of chalcones with internal alkynes: A DFT study","authors":"Xueli Mu ,&nbsp;Yihang Zhou ,&nbsp;Huaishen Li ,&nbsp;Jing Zhang ,&nbsp;Jian Zhang ,&nbsp;Kang Lv ,&nbsp;Tao Liu","doi":"10.1016/j.jorganchem.2025.123507","DOIUrl":"10.1016/j.jorganchem.2025.123507","url":null,"abstract":"<div><div>Computational studies were performed to provide mechanistic insights into the (4+1) carbocyclization mechanism from chalcones with internal alkynes catalyzed by rhodium catalysis. Computational results suggested that cationic rhodium (C<sub>p</sub><sup>t</sup>RhOAc<sup>+</sup>) was generally used as the active catalyst, and the generation of 2<em>H</em>-furanium salt can be divided into three stages: formation of pyrylium salt, hydrolysis, and 2<em>H</em>-furanium salt formation. The factors responsible for the regio-, chem- and stereo-selectivities are discussed. The regio- and chem-selectivity step is identified as the migratory insertion process in the first catalytic cycle. The reason can be understood from the electronic effect. The stereochemistry-determining-step is the migratory insertion process in the second catalytic cycle, which can be ascribed to the steric effect as RSS-<strong>TS<sub>21–22</sub></strong> identifies a more expansive structure.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1026 ","pages":"Article 123507"},"PeriodicalIF":2.1,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143309538","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}
引用次数: 0
The performance of metal carbon-based quantum dots as an anti-bacterial factor in green conditions
IF 2.1 3区 化学
Journal of Organometallic Chemistry Pub Date : 2024-12-30 DOI: 10.1016/j.jorganchem.2024.123495
Payam Ansari , Mahdieh Ghobadifard , Sajjad Mohebbi , Morahem Ashengroph
{"title":"The performance of metal carbon-based quantum dots as an anti-bacterial factor in green conditions","authors":"Payam Ansari ,&nbsp;Mahdieh Ghobadifard ,&nbsp;Sajjad Mohebbi ,&nbsp;Morahem Ashengroph","doi":"10.1016/j.jorganchem.2024.123495","DOIUrl":"10.1016/j.jorganchem.2024.123495","url":null,"abstract":"<div><div>Carbon quantum dots and metal-doped carbon quantum dots (N-CQDs and M-CQDs) were prepared by the hydrothermal method. The samples were characterized by EDS, UV–Vis, FT-IR, XRD, and PL techniques. FT-IR investigation demonstrates that M-CQDs have a shift of the peak associated with C-O and C=O oxygen bonds due to doping metals into carbon quantum dots, and a band at 550 cm<sup>-1</sup>, which is related to M-O bonds. N-CQDs and M-CQDs exhibited impressive <span><span>PL</span><svg><path></path></svg></span> behavior as an <span><span>antibacterial</span><svg><path></path></svg></span> factor against representative Gram-negative and Gram-positive bacterial strains. According to the findings and comparisons of the average halo zone of the anti-bactericidal activity of the prepared samples and MIC methods, N-CQDs and M-CQDs demonstrate excellent prevention versus bacteria with the best MIC of 0.5 mg/L. Co-CQDs had the greatest inhibitory effect against S. aureus with an average halo zone diameter of 15 mm, and E. coli with an average halo zone diameter of 13 mm. This toxicity is due to the generation of reactive oxygen species and the interaction between the M-CQDs and cells.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1026 ","pages":"Article 123495"},"PeriodicalIF":2.1,"publicationDate":"2024-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143309542","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}
引用次数: 0
Preparation of a series of heterobimetallic complexes containing bridging ethylidyne ligands by the reaction of diruthenium Bis(μ-ethylidyne) complex with 3d metal carbonyls: Alkylidyne−alkylidyne coupling reaction at the Ru2Fe site
IF 2.1 3区 化学
Journal of Organometallic Chemistry Pub Date : 2024-12-30 DOI: 10.1016/j.jorganchem.2024.123497
Naoya Noguchi, Toshiro Takao
{"title":"Preparation of a series of heterobimetallic complexes containing bridging ethylidyne ligands by the reaction of diruthenium Bis(μ-ethylidyne) complex with 3d metal carbonyls: Alkylidyne−alkylidyne coupling reaction at the Ru2Fe site","authors":"Naoya Noguchi,&nbsp;Toshiro Takao","doi":"10.1016/j.jorganchem.2024.123497","DOIUrl":"10.1016/j.jorganchem.2024.123497","url":null,"abstract":"<div><div>Diruthenium bis(μ-ethylidyne) complex [(Cp*Ru)<sub>2</sub>(μ-CMe)<sub>2</sub>] (<strong>1</strong>) reacts smoothly with metal carbonyls of group 6–9 3d metals to afford heterobimetallic tri- and tetranuclear complexes. While bis(ethylidyne) complexes [(Cp*Ru)<sub>2</sub>(μ-CMe)(μ<sub>3</sub>-CMe)(μ-CO)<sub>2</sub>{Cr(CO)<sub>3</sub>}] (<strong>2</strong>) and [(Cp*Ru)<sub>2</sub>(μ<sub>3</sub>-CMe)<sub>2</sub>(μ-CO){Fe(CO)<sub>3</sub>}] (<strong>4</strong>) were obtained by the reaction of <strong>1</strong> with [Cr(CO)<sub>6</sub>] and [Fe(CO)<sub>5</sub>], respectively, the reaction with [Mn<sub>2</sub>(CO)<sub>10</sub>] yielded μ-vinylidene−μ<sub>3</sub>-ethylidyne complex [(Cp*Ru)<sub>2</sub>(μ-C=CH<sub>2</sub>)(μ<sub>3</sub>-CMe)(μ-CO)<sub>2</sub>{Mn(CO)<sub>3</sub>}] (<strong>3</strong>) accompanied by the abstraction of a methyl proton by [Mn(CO)<sub>5</sub>]<sup>•</sup>. By the reaction with an excess amount of [Co<sub>2</sub>(CO)<sub>8</sub>], tetranuclear bis(μ<sub>3</sub>-ethylidyne) complex [(Cp*Ru)<sub>2</sub>(μ<sub>3</sub>-CMe)<sub>2</sub>(μ-CO){Co(CO)<sub>2</sub>}<sub>2</sub>] (<strong>6</strong>) was exclusively obtained. These reactions implied that the delocalized π-electrons in the [Ru<sub>2</sub>C<sub>2</sub>] core of <strong>1</strong> were used to construct the heterometallic skeleton with unsaturated organometallic species. Although complexes <strong>2</strong> and <strong>3</strong> underwent fragmentation upon gentle heating, <strong>4</strong> reacted with CO at 60 °C to yield μ<sub>3</sub>-η<sup>2</sup>(||)-butyne complex [(Cp*Ru)<sub>2</sub>(μ<sub>3</sub>-η<sup>2</sup>(||)-MeCCMe)(μ<sub>3</sub>-CO)(μ-CO){Fe(CO)<sub>3</sub>}] (<strong>5</strong>) via the alkylidyne−alkylidyne coupling. The density functional theory (DFT) calculations suggested that the C−C bond formation occurs via the intermediate containing μ- and μ<sub>3</sub>-ethylidyne ligands followed by the migration of the <em>m</em>-ethylidyne ligand across the Ru<sub>2</sub>Fe plane.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1026 ","pages":"Article 123497"},"PeriodicalIF":2.1,"publicationDate":"2024-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143309854","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}
引用次数: 0
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