Journal of Organometallic Chemistry最新文献

{"title":"DFT study on the mechanism and structural aspects of iron(II)-catalyzed condensation of epichlorohydrin and CO2","authors":"Alejandro Yañez-Cabrera ,&nbsp;Mario Sánchez ,&nbsp;Berenice Sampayo-Andrade ,&nbsp;Maribel Arroyo-Carranza ,&nbsp;Armando Ramírez-Monroy","doi":"10.1016/j.jorganchem.2024.123446","DOIUrl":"10.1016/j.jorganchem.2024.123446","url":null,"abstract":"<div><div>In this work, the catalytic cycle for the epichlorohydrin/CO₂ condensation using the [η⁵-(C₅H₅)Fe(CO)(L)]X complexes where L = NH₂(CH₂)₂PPh₂ and X <em>=</em> I (<strong>1</strong>), Br (<strong>2</strong>), Cl (<strong>3</strong>), OTf (<strong>4</strong>) and X = Br and L = NMe₂(CH₂)₂PPh₂ (<strong>7</strong>), NH₂(CH₂)₃PPh₂ (<strong>8</strong>), Py(CH₂)PPh₂ (<strong>9</strong>) and Py(PPh₂) (<strong>10</strong>), was studied computationally using density functional theory (DFT) at the ωB97xD/def2-TZVP level of theory. A good correlation between the optimized structures of complexes <strong>1</strong>–<strong>4</strong> and their respective X-ray diffraction (XRD) structures (used as experimental parameter) was found. Thus, the theoretical model was validated to study all the structures in the present work. The most thermodynamically and kinetically favored path for complexes <strong>1</strong>–<strong>4</strong> and <strong>8</strong>, bearing acid hydrogens, operates outside of the coordination sphere as an <em>ionic</em> pathway where the ionic intermediates are stabilized through hydrogen bonds. Catalyst <strong>2</strong> showed the most favored energy profile among complexes <strong>1</strong>–<strong>4</strong> at room temperature and at 80 °C, which supports the previously reported experimental results. This first computational approach also explains the catalytic activity of complexes <strong>1, 3</strong> and <strong>4</strong>. The most thermodynamically and kinetically favored path for complexes <strong>7, 9</strong>, and <strong>10</strong> was the <em>covalent</em> pathway which works in the inner sphere, with a metal-alkoxide and a metal-carbonate as intermediates. Computationally, catalyst <strong>10</strong> was the most active catalyst in the entire study, showing a completely spontaneous energy profile at room temperature, being of great relevance to be investigated experimentally. Finally, the chiral <strong><em>R</em>-</strong> and <strong><em>S</em></strong><em>-</em>[η⁵-(C₅H₅)Fe(CO)(H(Me)N(CH₂)₂PPh₂)]Br isomers, computationally built and optimized from complex <strong>2</strong>, were found to be highly favored stable isomers, also attractive for experimental research.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1024 ","pages":"Article 123446"},"PeriodicalIF":2.1,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142702844","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":"2,3-diferrocenyl-(1-triphenylphosphoranylidene)ketene: Synthesis and interactions with O, C, N, S, Se nucleophiles, characterization and X-ray diffraction","authors":"Claudia O. Oliva-Colunga,&nbsp;Jessica J. Sánchez García,&nbsp;Edgar A. Aguilar-Ortiz,&nbsp;Marcos Flores-Alamo,&nbsp;Lena Ruiz-Azuara,&nbsp;Elena I. Klimova","doi":"10.1016/j.jorganchem.2024.123441","DOIUrl":"10.1016/j.jorganchem.2024.123441","url":null,"abstract":"<div><div>The opening of the ring of 2,3-diferrocenylcyclopropenone <strong>1</strong> with triphenylphosphine was studied to obtain 2,3-diferrocenyl-(3-triphenylphosphoranylidene) ketene <strong>3</strong>. This was subsequently electrophile activated to react with different nucleophiles (<strong>O, C, N, S, Se</strong>) to obtain α,β-unsaturated carbonyl compounds with a preferable selectivity (<em>E</em>), which were stable under environmental conditions. The reduction reaction of the double bond of the α,β-unsaturated carbonyl compound was studied in the presence of hydrogen iodide. The structures of the synthesized compounds were established on the basis of data obtained from ¹H and ¹³C NMR spectroscopy and further confirmed by X-ray diffraction analysis.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1024 ","pages":"Article 123441"},"PeriodicalIF":2.1,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142703158","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":"Recyclable and reusable Pd(acac)2/BrettPhos/PEG-1000 system for the Suzuki-Miyaura coupling of nitroarenes","authors":"Qian Ye,&nbsp;Rong Liu,&nbsp;Li Wei,&nbsp;Mingzhong Cai","doi":"10.1016/j.jorganchem.2024.123442","DOIUrl":"10.1016/j.jorganchem.2024.123442","url":null,"abstract":"<div><div>Pd(acac)₂/BrettPhos in user-friendly polyethylene glycol (PEG-1000) is shown to be a highly efficient catalytic system for the Suzuki-Miyaura coupling of nitroarenes with arylboronic acids. The reaction proceeds smoothly at 130 °C with K₃PO₄·<em>n</em>H₂O as base without the use of 18-crown-6 as an additive, yielding a variety of functionalized unsymmetrical biaryls in good to high yields. The isolation of the products is facilely performed by the extraction with cyclohexane and more importantly, both expensive Pd(acac)₂ and BrettPhos in PEG-1000 system can be readily recycled and reused more than six times without a significant loss of catalytic efficiency.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1024 ","pages":"Article 123442"},"PeriodicalIF":2.1,"publicationDate":"2024-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142703156","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":"Deep-red or near-infrared-emitting Iridium (III) complex as efficient phosphorescent dye for live cell imaging through staining in cytoplasm","authors":"Sicheng Yao ,&nbsp;Yan Zhang ,&nbsp;Xinying Liu ,&nbsp;Xinyu Dong,&nbsp;Zhiming Zhang,&nbsp;Xingqiang Lü,&nbsp;Guorui Fu","doi":"10.1016/j.jorganchem.2024.123443","DOIUrl":"10.1016/j.jorganchem.2024.123443","url":null,"abstract":"<div><div>Despite the bioimaging highly realized from Ir(III)-complexes with visible-light, the staining on organelles by NIR-emissive (NIR = near infrared) Ir(III)-complex species especially in cytoplasm was rarely reported. In this work, two new cationic iridium (III) complexes ({[Ir(C^N)₂(N^N)]⁺ ·(PF₆)⁻}; C^<em>N</em> = 2,3-diphenylquinoxaline (<strong>dpqx</strong>)⁻ or 1-(benzo[b]-thiophen-2-yl)-isoquinoline (<strong>iqbt</strong>)⁻; N^<em>N</em> = 2-(pyridin-2-yl)-5-(4-vinylphenyl)pyridine (4vp-2,2′-bpy)), namely {[Ir(dpqx)₂(4vp-2,2′-bpy)]⁺ ·(PF₆)⁻} (<strong>1</strong>) and {[Ir(iqbt)₂(4vp-2,2′-bpy)]⁺ ·(PF₆)⁻} (<strong>2</strong>) with efficient deep-red (<span><math><msubsup><mi>λ</mi><mrow><mtext>em</mtext></mrow><mtext>Max</mtext></msubsup></math></span> = 630 nm, Φ_PL = 0.19) and NIR-emissions (<span><math><msubsup><mi>λ</mi><mrow><mtext>em</mtext></mrow><mtext>Max</mtext></msubsup></math></span> = 683 nm, Φ_PL = 0.16), are obtained, respectively. Moreover, beneficial from the excellent biocompatibility and low cytotoxicity, each of the two cationic iridium (III) complexes <strong>1</strong> and <strong>2</strong>, enables to exclusively stain in the cytoplasm of live cells. This research might provide two ideal candidates in the design of high-efficiency deep-red or NIR emitting cationic iridium (III) complexes for specific bioimaging agents.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1024 ","pages":"Article 123443"},"PeriodicalIF":2.1,"publicationDate":"2024-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142703157","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":"Recent advances on Pd schiff base catalysts in suzuki-miyaura cross-coupling reaction: A review","authors":"Iman Hussein Hasan ,&nbsp;Raed Muslim Mhaibes ,&nbsp;Abdul Amir H. Kadhum ,&nbsp;Hussein Ali Al-Bahrani ,&nbsp;Ali Thoulfikar A. Imeer ,&nbsp;Nihad A.M Al-Rashedi ,&nbsp;Guang Shu","doi":"10.1016/j.jorganchem.2024.123444","DOIUrl":"10.1016/j.jorganchem.2024.123444","url":null,"abstract":"<div><div>Carbon-carbon cross-coupling organic transformations are crucial in organic chemistry, but achieving them without a catalyst is challenging. Various catalysts based on complex have been developed to facilitate these reactions. Firstly, ligands based on phosphine were used, but their sensitive nature and toxic led researchers to turn to ligands based on Schiff base. These ligands are stable, simple to synthesize, and produce a variety of transition metal complexes. Ligands based on Schiff base are typically synthesized from the condensation reaction between carbonyl compounds and an amino group, and their complexes along with transition metal are widely used in different carbon–carbon cross-coupling organic transformations. In particular, palladium complexes, are well-known catalytic systems in carbon-carbon cross-coupling organic transformations such as the Suzuki-Miyaura cross-coupling organic transformations. This review focuses on the application of Pd Schiff base ligands in Suzuki-Miyaura reaction.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1024 ","pages":"Article 123444"},"PeriodicalIF":2.1,"publicationDate":"2024-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142703155","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":"Recent advances in homogeneous catalysts for the acceptorless dehydrogenation of alcohols to ketones and aldehydes","authors":"Dhrubajit Borah ,&nbsp;Abhilash Sharma ,&nbsp;Rekha Rani Dutta ,&nbsp;Indrani Bhuyan ,&nbsp;Rupjyoti Dutta","doi":"10.1016/j.jorganchem.2024.123445","DOIUrl":"10.1016/j.jorganchem.2024.123445","url":null,"abstract":"<div><div>Oxidant-free oxidation, also known as acceptorless dehydrogenation, has emerged as a powerful strategy for the oxidation of alcohols. Besides yielding carbonyl compounds, the method produces hydrogen gas- a promising green fuel with water as the only by-product. The elimination of toxic and stoichiometric oxidants or hydrogen acceptors makes this approach attractive from the standpoint of green and sustainable chemistry. Consequently, several transition metals-based catalytic methods have been developed to synthesise ketones and aldehydes through this green method. In this review, we would like to summarise the recent development of homogeneous catalysts for the acceptorless dehydrogenation of primary and secondary alcohols to yield aldehydes and ketones, respectively. Also, we delve into the specific roles played by various ligands, including bi-functional ligands, in fine-tuning the stereo-electronic properties of the metal catalyst and delineate their impact on reaction outcomes.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1024 ","pages":"Article 123445"},"PeriodicalIF":2.1,"publicationDate":"2024-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142703154","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":"Direct CO2 hydrogenation over Na and CeO2-promoted Iron and Cobalt-based Catalysts Supported on MCM-41","authors":"Aryane A. Marciniak ,&nbsp;Antonio E.C. Santos ,&nbsp;Hugo C. Reis ,&nbsp;Evelyn C.S. Santos ,&nbsp;Claudio J.A. Mota","doi":"10.1016/j.jorganchem.2024.123440","DOIUrl":"10.1016/j.jorganchem.2024.123440","url":null,"abstract":"<div><div>This contribution has studied iron or cobalt-based Fischer-Tropsch catalysts, promoted with CeO₂ and Na and supported on MCM-41 mesoporous silica in the direct CO₂ hydrogenation to hydrocarbons. The cobalt-based catalyst is more active in the presence of ceria as a promoter, presenting long-chain hydrocarbons under reaction conditions of 350 °C, 40 bar, H₂/CO₂ = 3, and GHSV = 6000 mL g^-1 h^-1. The characterization of the catalysts suggests that CoCeNa/M exhibits a strong Co-O-Si bond formation, preventing the cobalt oxide reduction to Co²⁺ species, which can be associated with methane production. On the other hand, iron-based catalysts present higher CO and CH₄ concentrations, as shown via in situ DRIFTS, suggesting a possible iron carbide phase, which can be formed by the severe FTS reaction conditions, producing a high concentration of water and competing with Sabatier reaction.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1023 ","pages":"Article 123440"},"PeriodicalIF":2.1,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142652595","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":"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}