Journal of Organometallic Chemistry最新文献

{"title":"Mechanistic and thermodynamic studies on directing group-assisted copper-catalyzed α-C(sp2)−H amination of aryl amines with alkylamines","authors":"Jinglei Cui,&nbsp;Wenrui Zheng,&nbsp;Peilei Jiao,&nbsp;Hao Jin","doi":"10.1016/j.jorganchem.2024.123400","DOIUrl":"10.1016/j.jorganchem.2024.123400","url":null,"abstract":"<div><div>In mechanistic, three possible pathways of α-C(sp[<span><span>2</span></span>])<strong>−</strong>H functionalization amination of picolinamide with morpholine catalyzed by Cu(OAc)₂/O₂ in p-xylene were studied. Through theoretical calculations, it was found that the pathway involving the radical-cation intermediates produced by the subsequent single electron transfer (SET) was proved to be the most favorable. Then, we also discussed the solvation and substituent effects of three key steps, including N − H bond deprotonation, C − N bond formation rate-determining step and C − H bond deprotonation step, so as to fully understand the mechanism of directing group-assisted copper-catalyzed α-C <strong>−</strong> H functionalization of aniline and the screening of substrates and solvents. In thermodynamic, the SET process plays a crucial role in the entire catalytic cycle. Therefore, we further studied the reduction potential (<em>E_red</em>) values of Cu(II) radical-cation intermediates involved in the SET process, reflecting the occurrence trend of SET from the thermodynamic point of view, and studied the substituent effects and structure-activity relationships on <em>E_red</em> values of Cu(II) complexes derivatives formed by different Cu(Ⅱ) catalysts, different directing groups, different alkylamines and aromatic amines substrates. It is also found that there are many quantitative structure-activity relationships between <em>E_red</em> and the singly occupied molecular orbital (SOMO) energy, Hammett substituent constant σ⁺ and other structural parameters.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1022 ","pages":"Article 123400"},"PeriodicalIF":2.1,"publicationDate":"2024-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142314269","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":"In Situ generated PdNPs immobilized on polystyrene supported DABCO Dicationic ionic liquid: An efficient and reusable catalyst for Suzuki and Heck coupling reactions","authors":"Archana Rajmane ,&nbsp;Jasbir Mahey ,&nbsp;Sumit Kamble ,&nbsp;Arjun Kumbhar","doi":"10.1016/j.jorganchem.2024.123390","DOIUrl":"10.1016/j.jorganchem.2024.123390","url":null,"abstract":"<div><div>A catalyst named PdNPs-DDIL@PS has been synthesized by immobilizing PdNPs on a DABCO Dicationic Ionic Liquid (DDIL) supported on Merrifield Resin (PS). The PdNPs (∼4.16 nm size) generated <em>in situ</em> were fully characterized using different techniques such as SEM, TEM, TGA-DTA, and XPS. It has been found that the catalyst is highly active in the Suzuki coupling reaction of various aryl bromides and aryl boronic acids in 70 % aqueous ethanol at room temperature. The catalyst produced the desired Suzuki coupling products in good to excellent yields. Additionally, the protocol was extended for the Heck coupling reactions in DMF at 80 °C with good to excellent yields. The catalyst attained a good turnover number (TON) of 160.00–189.92 and a turnover frequency (TOF) of 8.493–18.992 min⁻¹ for the Suzuki and TON of 173.33–189.77 and TOF of 3.952–6.325 min⁻¹ for the Heck coupling reactions. The catalyst displayed at least four times recyclability for the Suzuki coupling without a substantial decrease in product yields. Additionally, it boosts impressive environmentally-friendly credentials in Suzuki coupling reactions.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1022 ","pages":"Article 123390"},"PeriodicalIF":2.1,"publicationDate":"2024-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142425590","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":"Role of organometallic complexes in targeted therapies of different diseases: Infectious diseases, cancer and neurodegenerative Diseases","authors":"Nitin V ,&nbsp;Tanmay Anand ,&nbsp;Chandra Kant Singh ,&nbsp;Kushneet Kaur Sodhi","doi":"10.1016/j.jorganchem.2024.123389","DOIUrl":"10.1016/j.jorganchem.2024.123389","url":null,"abstract":"<div><div>Organometallic complexes have garnered attention in the design of metal chemotherapeutics in recent years because of their exceptional stability and distinct characteristics when compared to conventional coordination complexes. Organometallic complexes are perfect for regulating drug release and improving cellular uptake because of their redox potentials, ligand exchange kinetics, and distinctive reactivity profiles. Many studies have been conducted to investigate the antiviral, anticancer, antibacterial, antifungal, and antiparasitic activities of metal complexes. Numerous complexes possessing intriguing biological characteristics have been created. Significantly, several disorders are treated with specific metal complexes. An overview of the organometallics used in medicine, particularly those with antimicrobial and anti-cancer capabilities, complexes used to treat neurological illnesses, and difficulties encountered in this specific field, have been presented in this work. This review's main goal is to give readers an overview of the noteworthy advancements of organometallics made in each of these many medical specialties.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1022 ","pages":"Article 123389"},"PeriodicalIF":2.1,"publicationDate":"2024-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142327761","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":"Sustainable synthesis of benzimidazoles catalyzed by recyclable functionalized organosilica","authors":"Fatemeh Rajabi ,&nbsp;Alexandra Golubenkova ,&nbsp;Rafael Luque","doi":"10.1016/j.jorganchem.2024.123387","DOIUrl":"10.1016/j.jorganchem.2024.123387","url":null,"abstract":"<div><div>A highly efficient protocol is herein reported for the preparation of benzimidazole compounds from o-phenylenediamine and various benzaldehyde derivatives in the presence of heterogeneous pyridinium protic ionic liquids supported on periodic mesoporous organosilica (PMO) in water. The synthesis of three novel benzimidazole derivatives is also reported. The proposed approach successfully afforded products in good yield under mild reaction conditions. PMO-Py-IL exhibited excellent catalyst activity and reusability for at least ten reaction cycles with no significant activity loss.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1022 ","pages":"Article 123387"},"PeriodicalIF":2.1,"publicationDate":"2024-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142314268","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 backbone linker (O vs NH) on the ability of pincer-supported nickel hydrides to reduce CO2","authors":"Mahmood Ahmadianpoor,&nbsp;Patrick D. Pridemore,&nbsp;Jeanette A. Krause,&nbsp;Hairong Guan","doi":"10.1016/j.jorganchem.2024.123399","DOIUrl":"10.1016/j.jorganchem.2024.123399","url":null,"abstract":"<div><div>The reactivity of nickel hydrides supported by a pincer ligand often can be tuned by modifying the ligand at the three donor sites. In this study, ligand modification is made at the backbone, more specifically the linkers X and Y in {2,6-C₆H₃(XP^tBu₂)(YP^tBu₂)}NiH. Of the three nickel hydrides investigated herein, the PNCNP-pincer complex (X = Y = NH) is the most reactive one towards CO₂, whether it is for the rate of CO₂ capture from air or for the thermodynamic favorability of CO₂ insertion into the Ni–H bond. The POCOP-pincer complex (X = Y = O) is the least reactive hydride whereas the POCNP-pincer complex (X = O, Y = NH) is ranked in the middle. To have access to the hybrid pincer complex, an improved synthetic method for the proligand, <em>m</em>-C₆H₄(OP<em>^t</em>Bu₂)(NHP<em>^t</em>Bu₂), is also developed.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1022 ","pages":"Article 123399"},"PeriodicalIF":2.1,"publicationDate":"2024-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0022328X24003942/pdfft?md5=180063fe883fa16f3bb3c1113ec0b235&pid=1-s2.0-S0022328X24003942-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142314267","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}

{"title":"NO bond cleavage and N2 activation reactions of the Nitrosyl-Bridged complex [Mo2Cp2(µ-PtBu2)(µ-NO)(NO)2]","authors":"M. Angeles Alvarez,&nbsp;M. Esther García,&nbsp;Daniel García-Vivó,&nbsp;Ana M. Guerra,&nbsp;Miguel A. Ruiz","doi":"10.1016/j.jorganchem.2024.123375","DOIUrl":"10.1016/j.jorganchem.2024.123375","url":null,"abstract":"<div><p>The title compound was prepared through a three-step procedure starting with the hydride complex [Mo₂Cp₂(µ-H)(µ-P<em>^t</em>Bu₂)(CO)₄], which was first dehydrogenated through reaction with HBF₄·OEt₂ to give the unsaturated complex [Mo₂Cp₂(µ-P<em>^t</em>Bu₂)(CO)₄](BF₄) (Mo=Mo), which displays a transoid structure according to experimental (Mo-Mo = 2.8283(7) Å) and Density Functional Theory studies. The latter was then reacted with NO to give the dinitrosyl derivative [Mo₂Cp₂(µ-P<em>^t</em>Bu₂)(CO)₂(NO)₂](BF₄), which in turn was further decarbonylated and nitrosylated upon reaction with [N(PPh₃)₂]NO₂ to give the title nitrosyl-bridged complex (Mo-Mo = 2.905(1) Å). This complex displayed a structure comparable to that of its PCy₂-bridged analogue, with similar pyramidalization of the bridging nitrosyl, but a more pronounced folding of the central MoPMoN skeleton and bending of terminal nitrosyls. It also displayed a similar N<img>O bond activation chemistry, as shown by its reactions with HBF₄·OEt₂ to give the nitroxyl-bridged complex [Mo₂Cp₂(µ-P<em>^t</em>Bu₂)(µ-<em>k</em>¹:<em>η</em>²-HNO)(NO)₂](BF₄) (HN<img><em>O</em> = 1.330(8) Å), with P(OEt)₃ to give the phosphoraniminate-bridged complex [Mo₂Cp₂(µ-P<em>^t</em>Bu₂){µ-NP(OEt)₃}(NO)₂], and with Na(Hg) to give the amide-bridged derivative [Mo₂Cp₂(µ-P<em>^t</em>Bu₂)(µ-NH₂)(NO)₂]. Under a nitrogen atmosphere, however, the latter reaction also gave a minor side product identified as the dinitrogen-bridged derivative [Mo₄Cp₄(µ-P<em>^t</em>Bu₂)₂(µ₄-N₂)(NO)₄]. This tetranuclear complex displays a dinitrogen molecule bridging four metal atoms in the novel µ₄-<em>k</em>¹:<em>k</em>¹:<em>k</em>¹:<em>k</em>¹ coordination mode, with strong metal-nitrogen interactions taking the N₂ ligand to the diazendiide (N₂^2-) limit (N<img><em>N</em> = 1.241(3) Å).</p></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1022 ","pages":"Article 123375"},"PeriodicalIF":2.1,"publicationDate":"2024-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0022328X2400370X/pdfft?md5=e97261e693c80a6c2cee6b7b3f6eabe0&pid=1-s2.0-S0022328X2400370X-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142271182","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}

{"title":"Controlling quantum interference patterns in redox-active rings","authors":"Lucy E. Wilson ,&nbsp;Thomas T.C. Yue ,&nbsp;Michael S. Inkpen ,&nbsp;Iain Grace ,&nbsp;Andrew J.P. White ,&nbsp;Colin Lambert ,&nbsp;Tim Albrecht ,&nbsp;Nicholas J. Long","doi":"10.1016/j.jorganchem.2024.123368","DOIUrl":"10.1016/j.jorganchem.2024.123368","url":null,"abstract":"<div><div>The ability to create molecules, which exhibit tunable and unique conductive properties is a key requirement for the development of future generation devices. Towards this concept, we herein report synthetic routes to novel linear, branched, and cyclic Ru(1,2-bis(diphenylphosphino)ethane)₂-containing molecules, including the variation of surface binding groups. Synthetic strategies are discussed followed by a discussion of the electrochemical properties of the molecules. Theoretical calculations suggest that cyclic derivatives exhibit higher conductance compared to their linear counterparts due to quantum interference effects. Additionally, the conductance of both linear and cyclic molecules can vary depending on their orientation.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1022 ","pages":"Article 123368"},"PeriodicalIF":2.1,"publicationDate":"2024-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142358168","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}

{"title":"Synthesis, structural characterization and computational studies of half- sandwich Ru(II) (η6-p–cymene) TPA appended benzhydrazone complex","authors":"Raj Kumar Ramasamy ,&nbsp;Jan Grzegorz Małecki","doi":"10.1016/j.jorganchem.2024.123382","DOIUrl":"10.1016/j.jorganchem.2024.123382","url":null,"abstract":"<div><div>A ruthenium complex of the type Ru[<em>η</em>⁶(<em>p</em>–cymene)Cl(L)] where <em>L</em> = Triphenylamine (TPA) appended O^N bidendate benzhydrazone ligand was synthesized and characterized by various analytical and spectral [UV, FT-IR, NMR (¹H and ¹³C) and HRMS] methods. The solid state molecular structure of the ruthenium complex was investigated with the aid of X-ray crystallography results with pseudo-octahedral geometry around the metal centre. FT-IR spectroscopy confirms the coordination <em>via</em> the azomethine nitrogen and imidolate oxygen. Density Functional theory (DFT) calculations have been used to analyse the composition of frontiers orbitals. The bonding interactions between the ligand and ruthenium complex fragments have been examined by EDA. The spin-allowed singlet transitions were calculated with the TD-DFT method. NBO analysis shows that the donation from ligand to metal has value of 136.64 kcal/mol and the back donation is equal to 109.61 kcal/mol. Hence the ligand is a σ-donor with weak π-acceptor properties. The DOS spectrum of both ligand and complex were plotted in terms of Mullikan population analysis were calculated using the GassSum program. Further, the relative contributions to the Hirshfeld surface area for the various close intermolecular contacts of ruthenium complex are investigated and H…H interactions plays an important role for the construction of the crystal structure of the ruthenium complex.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1022 ","pages":"Article 123382"},"PeriodicalIF":2.1,"publicationDate":"2024-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142320229","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":"Mn2(CO)10 catalyzed visible-light-promoted synthesis of 1H-pyrazole-4-carboxamides; A sustainable multi-component statergy with antibacterial and cytotoxic evaluations","authors":"Santhosh Govindaraju ,&nbsp;Sankar Ganesh Ramaraj ,&nbsp;Anushka Servesh ,&nbsp;J. Rajprasad ,&nbsp;Niraj Kumar ,&nbsp;Vivekananthan Sadaiyandi ,&nbsp;Sumaiya Tabassum","doi":"10.1016/j.jorganchem.2024.123384","DOIUrl":"10.1016/j.jorganchem.2024.123384","url":null,"abstract":"<div><p>Multicomponent reactions play a pivotal role in synthesizing 1<em>H</em>-pyrazole-4-carboxamides, underscoring its significance in sustainable organic synthesis. These compounds, valued for their diverse biological activities, have garnered substantial attention in pharmaceutical research. A facile, rapid one-pot strategy to access an extensive array of 1<em>H</em>-pyrazole-4-carboxamide derivatives, utilizing substituted aldehydes, cyanoacetamide, and hydrazine hydrate as substrates and a readily accessible Mn₂(CO)₁₀ as photocatalyst in EL: H₂O (1:1). Among the synthesized series, products 4b, 4 g, 4k showed remarkable antibacterial activity against <em>E coli, P aeruginosa, S. aureus</em> in agar medium and excellent cytotoxicity with Human colorectal carcinoma (HCT-116), Liver cancer cells (Hep-G2) and breast adenocarcinoma (MCF-7) cell lines. The current method is characterized by its affordability, non-toxicity, easy access to starting materials, and notably with minimal waste generation. Additionally, remarkable aspects include its mild operating conditions, environmentally friendly nature, and the ability to accommodate a wide range of both electron-donating and electron-withdrawing groups.</p></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1022 ","pages":"Article 123384"},"PeriodicalIF":2.1,"publicationDate":"2024-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0022328X24003796/pdfft?md5=d8f5c3123e42ff07a2804d4e177e82d1&pid=1-s2.0-S0022328X24003796-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142271181","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}

{"title":"Polyaniline/cupric oxide organometallic nanocomposites as a sonocatalyst for the degradation of methylene blue: Experimental study, RSM optimization, and DFT analysis","authors":"Ahmed Boucherdoud ,&nbsp;Djamal Eddine Kherroub ,&nbsp;Khedidja Dahmani ,&nbsp;Oukacha Douinat ,&nbsp;Abdelkarim Seghier ,&nbsp;Benaouda Bestani ,&nbsp;Noureddine Benderdouche","doi":"10.1016/j.jorganchem.2024.123386","DOIUrl":"10.1016/j.jorganchem.2024.123386","url":null,"abstract":"<div><p>In this study, an organometallic nanocomposite consisting of polyaniline (PANI) and copper oxide (CuO) was synthesized using the in-situ polymerization method of aniline, with copper chloride serving as a polymerization catalyst and precursor, along with sodium hydroxide to synthesize CuO nanoparticles. Various techniques were employed to characterize the synthesized nanocomposite, including Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), UV-vis spectroscopy, scanning electron microscopy (SEM), and determination of pH of the point of zero charge (pH_pzc). The catalytic performance of the PANI/CuO nanocomposite was evaluated for the degradation of methylene blue (MB), both with and without ultrasonic irradiation. The nanocomposite catalyst exhibited significantly improved catalytic efficiency for MB degradation in ultrasonic irradiation, compared to degradation without ultrasonic irradiation. The experimental conditions were optimized using the Box-Behnken Design (BBD), resulting in finding that the highest MB degradation efficiency reached 95% under ultrasonic irradiation and 74% without it. These results were achieved with a dye concentration of 50 mg/L, a catalyst dose of 0.4 mg/L, and a contact time of 60 minutes. Theoretical calculations suggest that BM molecules promote an attacking mode owing to their electrophilic characteristics, which make them more likely to accept electrons. This propensity leads to the formation of an antibonding orbital in conjunction with PAN/CuO, indicating a synergistic effect between organic molecules (PANI) and inorganic nanoparticles (CuO). This synergistic effect enhances the catalytic activity. Furthermore, the catalyst has demonstrated excellent reusability and stability, suggesting its potential application as an efficient PANI/CuO nanocomposite catalyst for the removal of organic pollutants.</p></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1022 ","pages":"Article 123386"},"PeriodicalIF":2.1,"publicationDate":"2024-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142271184","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}