Organometallics最新文献_第3页

Ni-Catalyzed ZnCl2–Assisted Domino Coupling of Enones and Alkyne-Tethered Vinylcyclopropanes via C–C Bond Cleavage of Cyclopropane 镍催化 ZnCl2 通过环丙烷的 C-C 键裂解作用辅助烯酮和炔烃拴乙烯基环丙烷的多米诺偶联反应

IF 2.5 3区化学

Organometallics Pub Date : 2024-10-03 DOI: 10.1021/acs.organomet.4c0034110.1021/acs.organomet.4c00341

Mika Sakazaki, and , Shin-ichi Ikeda*,

{"title":"Ni-Catalyzed ZnCl2–Assisted Domino Coupling of Enones and Alkyne-Tethered Vinylcyclopropanes via C–C Bond Cleavage of Cyclopropane","authors":"Mika Sakazaki,  and , Shin-ichi Ikeda*, ","doi":"10.1021/acs.organomet.4c0034110.1021/acs.organomet.4c00341","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00341https://doi.org/10.1021/acs.organomet.4c00341","url":null,"abstract":"A Ni-catalyzed, ZnCl2-assisted domino coupling of enones and alkyne-tethered vinylcyclopropanes (VCPs) was developed. The reaction proceeds through the following steps: (1) oxidative cyclization of a Ni(0) complex with an enone and the alkyne component of the alkyne-tethered VCP in the presence of ZnCl2, (2) carbonickelation of the VCP moiety, (3) β-C elimination leading to C–C bond cleavage of the cyclopropane moiety, and (4) β-H elimination to stereoselectively obtain (E)-1,3-diene as the coupling product. The optimal reaction conditions and scope of enones and alkyne-tethered VCPs were systematically explored. The reaction mechanism was investigated by performing deuterium-labeling experiments and density functional theory (DFT) calculations on the model compounds. The results clarify that the β-C elimination process occurs readily, and the Ni(0) precatalyst is regenerated via the 1,4-addition of H–Ni(II) species, generated by β-H elimination, to an excess of enone, followed by Zn reduction of the formed 1,4-adduct.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.5,"publicationDate":"2024-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142436979","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

Functionalization Strategy in 2D Flexible Zn(BTTB)-MOF for Improving Storage and Release of Anticancer Drugs: A Comprehensive Computational Investigation 二维柔性 Zn(BTTB)-MOF中用于改善抗癌药物储存和释放的功能化策略：全面的计算研究

IF 2.5 3区化学

Organometallics Pub Date : 2024-09-30 DOI: 10.1021/acs.organomet.3c0053510.1021/acs.organomet.3c00535

Shabnam Naderlou*, Morteza Vahedpour and Douglas M. Franz,

{"title":"Functionalization Strategy in 2D Flexible Zn(BTTB)-MOF for Improving Storage and Release of Anticancer Drugs: A Comprehensive Computational Investigation","authors":"Shabnam Naderlou*, Morteza Vahedpour and Douglas M. Franz, ","doi":"10.1021/acs.organomet.3c0053510.1021/acs.organomet.3c00535","DOIUrl":"https://doi.org/10.1021/acs.organomet.3c00535https://doi.org/10.1021/acs.organomet.3c00535","url":null,"abstract":"A multiscale computational approach was used to investigate the interaction, adsorption, and diffusion of three anticancer drugs, 5-fluorouracil (5-FU), busulfan (BU), and cisplatin (CIS), within the pores of a 2D flexible Zn-based MOF (Zn(BTTB)-MOF) functionalized with –NH2, –NO2, −OH, and -SH groups. The DFT analysis results indicated that adding functional groups to the H3BTTB organic linker created additional binding sites, resulting in stronger interactions between the drugs and the modified structures by 17.5% for NO2–Zn(BTTB)-MOF···5-FU to 115% for OH-Zn(BTTB)-MOF···BU in binding energies. Our grand canonical Monte Carlo (GCMC) studies revealed that both functionalized and pristine structures exhibited a high drug-loading capacity, increasing to ∼13, 15, and 24% for CIS, 5-FU, and BU, respectively. Molecular dynamics (MD) simulations indicated a decrease in the dynamics of the modified structures as a function of simulation time, with calculated diffusion coefficients ranging from (0.78–15.4) × 10–12 m2·s–1, consistent with previous findings in drug release. The study highlights the significance of adding functional groups to the Zn(BTTB)-MOF organic linker, as it significantly enhances the binding energy of anticancer drugs. Functionalized Zn(BTTB)-MOF enhances drug interactions due to additional binding sites, increasing drug-loading capacity and resulting in slower drug diffusion, making it more effective for anticancer drug delivery.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.5,"publicationDate":"2024-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142437337","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

Hydrogen Production from Aqueous Formic Acid through the Ligand Design Strategy in Half-Sandwich Ruthenium Complexes 通过半三明治钌配合物配体设计策略从甲酸水溶液中制氢

IF 2.5 3区化学

Organometallics Pub Date : 2024-09-30 DOI: 10.1021/acs.organomet.4c0035710.1021/acs.organomet.4c00357

Sanjeev Kushwaha, Tushar A. Kharde, Ralf Köppe and Sanjay Kumar Singh*,

{"title":"Hydrogen Production from Aqueous Formic Acid through the Ligand Design Strategy in Half-Sandwich Ruthenium Complexes","authors":"Sanjeev Kushwaha, Tushar A. Kharde, Ralf Köppe and Sanjay Kumar Singh*, ","doi":"10.1021/acs.organomet.4c0035710.1021/acs.organomet.4c00357","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00357https://doi.org/10.1021/acs.organomet.4c00357","url":null,"abstract":"Herein, we synthesized water-soluble ruthenium complexes [(η6-p-cymene)Ru(κ2-L)]+ ([C-1]–[C-5]) ligated with substituted bis-imidazole methane-based ligands (L1–L5) and the molecular structures of the representative complexes [C-2] and [C-4] were established by single-crystal X-ray diffraction. We screened the synthesized complexes for the catalytic dehydrogenation of formic acid (FA) in water, where substitution on the bis-imidazole methane ligands was found to exert a significant impact on the catalytic activity of the complexes. The results inferred that, among the screened catalysts, [C-5] outperformed others with an initial turnover frequency (TOF) of 1831 h–1 at 90 °C. One of the most notable features of [C-5] was its exceptional long-term stability, as it maintained efficient H2 production from FA for 35 catalytic runs and remained active even after 60 days without any significant deactivation, reaching a turnover number (TON) of 35,000. Furthermore, reaction kinetics and the influence of various reaction parameters are thoroughly examined; comprehensive mass and NMR investigations under both catalytic and control conditions are conducted, and theoretical studies are performed to gain more insights into the reaction pathway of FA dehydrogenation over the studied catalysts.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.5,"publicationDate":"2024-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142437587","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

Selectivity of Ru and Fe PR2NR’2 Catalysts Toward Acceptorless Dehydrogenation of Benzylamine Ru 和 Fe PR2NR'2 催化剂对苯甲胺无受体脱氢反应的选择性

IF 2.5 3区化学

Organometallics Pub Date : 2024-09-29 DOI: 10.1021/acs.organomet.4c0034510.1021/acs.organomet.4c00345

Amrit S. Nanuwa, Matthew D. Hoffman, Kiran Nandi and Johanna M. Blacquiere*,

{"title":"Selectivity of Ru and Fe PR2NR’2 Catalysts Toward Acceptorless Dehydrogenation of Benzylamine","authors":"Amrit S. Nanuwa, Matthew D. Hoffman, Kiran Nandi and Johanna M. Blacquiere*, ","doi":"10.1021/acs.organomet.4c0034510.1021/acs.organomet.4c00345","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00345https://doi.org/10.1021/acs.organomet.4c00345","url":null,"abstract":"The performance of six ruthenium catalysts and two iron catalysts were evaluated toward the acceptorless dehydrogenation of benzylamine. All catalysts shared the common structure [M(Cp/Cp*)(PR2NR’2)(MeCN)]PF6 (M = Fe, Ru; Cp = cyclopentadienyl; Cp* = 1,2,3,4,5-pentamethylcyclopentadienyl; PR2NR’2 = 1,5-R′-3,7-R-1,5-diaza-3,7-diphosphacyclooctane) in which the PR2NR’2 ligands contain a pendant tertiary amine that enables cooperative catalytic mechanisms. Catalytic activity and selectivity were evaluated to identify the optimal catalyst structural features. The iron catalyst [Fe(Cp)(PPh2NPh2)(MeCN)]PF6 demonstrated near-exclusive selectivity for the acceptorless dehydrogenative coupled product, N-benzylidenebenzylamine. The absence of the hydrogen-borrowed (dibenzylamine) product indicates that this iron catalyst strongly favors dehydrogenation pathways over hydrogenation. This was confirmed through the control reactions. The performance of [Fe(Cp)(PPh2NPh2)(MeCN)]PF6 was optimized, but the catalyst was ineffective toward a broader scope of substrates.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.5,"publicationDate":"2024-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142430712","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

Pnictogen Bonding at the Core of a Carbene-Stiborane-Gold Complex: Impact on Structure and Reactivity 碳-锡硼烷-金复合物核心的正锑结合：对结构和反应活性的影响

IF 2.5 3区化学

Organometallics Pub Date : 2024-09-26 DOI: 10.1021/acs.organomet.4c0034710.1021/acs.organomet.4c00347

Paula Castro Castro, and , François P. Gabbaï*,

引用次数: 0

Pnictogen Bonding at the Core of a Carbene-Stiborane-Gold Complex: Impact on Structure and Reactivity. 碳烯-锡硼烷-金复合物核心的正锑结合：对结构和反应活性的影响。

IF 2.5 3区化学

Organometallics Pub Date : 2024-09-26 eCollection Date: 2024-10-14 DOI: 10.1021/acs.organomet.4c00347

Paula Castro Castro, François P Gabbaï

引用次数: 0

Direct Formic Acid Production by CO2 Hydrogenation with Ir Complexes in HFIP under Supercritical Conditions 在超临界条件下利用 HFIP 中的铱络合物通过二氧化碳加氢直接生产甲酸

IF 2.5 3区化学

Organometallics Pub Date : 2024-09-24 DOI: 10.1021/acs.organomet.4c0022910.1021/acs.organomet.4c00229

Seo Ono, Ryoichi Kanega and Hajime Kawanami*,

{"title":"Direct Formic Acid Production by CO2 Hydrogenation with Ir Complexes in HFIP under Supercritical Conditions","authors":"Seo Ono, Ryoichi Kanega and Hajime Kawanami*, ","doi":"10.1021/acs.organomet.4c0022910.1021/acs.organomet.4c00229","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00229https://doi.org/10.1021/acs.organomet.4c00229","url":null,"abstract":"Development of hydrogen energy carriers is crucial for society. Reversible (de)hydrogenation using carbon-based materials, particularly formic acid (FA), has been widely studied. Typically produced under basic conditions through CO2 hydrogenation, formate salt is an energetically favorable form, but its dehydrogenation is challenging. This study found an equilibrium between formic acid dehydrogenation (FADH) and CO2 hydrogenation under high-pressure conditions, facilitated organic solvent suppression of dehydrogenation, and accelerated hydride formation on an Ir catalyst. These conditions allow for the direct production of FA from CO2 and H2 in nonbasic 1,1,1,3,3,3-hexafluoropropan-2-ol (HFIP) using a pentamethylcyclopentadienyl iridium (Cp*Ir) catalyst featuring a 4,4′-diamino-2,2′-bipyridine ligand (4DABP). Under mild conditions (50 °C, 1 MPa; CO2:H2 ratio = 1:1), the catalyst achieved a turnover number (TON) of 2084 in 2 h. The use of supercritical CO2 further increased the TON to 6100, producing a 0.12 M FA solution after 96 h. This study presents a novel method for the direct production of formic acid from CO2 and H2, indicating new possibilities in the development of hydrogen energy carriers.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.5,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142430666","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

One-Pot Fe-Catalyzed Pheromone Synthesis Via C1-Homologation of Unsymmetrical α,ω-Dihalogenated Derivatives with an Even Number of Carbon Atoms 通过碳原子数为偶数的非对称 α、ω-二卤代衍生物的 C1-同系物，实现铁催化的单锅费洛蒙合成反应

IF 2.5 3区化学

Organometallics Pub Date : 2024-09-24 DOI: 10.1021/acs.organomet.4c0034610.1021/acs.organomet.4c00346

Adrien Tintar, Pablo Chourreu, Olivier Guerret, Eric Gayon and Guillaume Lefèvre*,

{"title":"One-Pot Fe-Catalyzed Pheromone Synthesis Via C1-Homologation of Unsymmetrical α,ω-Dihalogenated Derivatives with an Even Number of Carbon Atoms","authors":"Adrien Tintar, Pablo Chourreu, Olivier Guerret, Eric Gayon and Guillaume Lefèvre*, ","doi":"10.1021/acs.organomet.4c0034610.1021/acs.organomet.4c00346","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00346https://doi.org/10.1021/acs.organomet.4c00346","url":null,"abstract":"We report in this work the optimization of a one-pot, four-step coupling sequence allowing stereoselective formation of alkyl-alkenyl linkages under iron catalysis at a low 0.25% load starting from difunctionalized electrophiles. A key tandem C1 homologation step followed by an iron-catalyzed Kumada alkyl-alkenyl cross-coupling is included in this sequence, allowing the direct obtention of an aliphatic nucleophile with an odd number of carbon atoms, bearing a terminal magnesium alkoxide function. The latter group acts as an in situ generated endogenous additive in the subsequent coupling step, bypassing the need for engineered ligands. Overall, this report affords a cheap and efficient way to generate odd-numbered coupling partners which usually request multistep preparation, along with their use in one-pot coupling syntheses using an Earth-abundant metal. Several applications to the obtention of targets of agrochemical interest are also described.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.5,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142517689","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 Evaluation of Trialkyl Ammonium Tetrakis(perfluorophenyl) Aluminate, a Highly Efficient Activator for High-Temperature Ethylene-α-Olefin Copolymerization Reactions 高温乙烯-α-烯烃共聚反应的高效活化剂三烷基四（全氟苯基）铝酸铵的合成与评估

IF 2.5 3区化学

Organometallics Pub Date : 2024-09-23 DOI: 10.1021/acs.organomet.4c0026810.1021/acs.organomet.4c00268

Sean Bremer, Robert J. Bellair, Travis W. Scholtz, Todd D. Senecal* and Jerzy Klosin*,

{"title":"Synthesis and Evaluation of Trialkyl Ammonium Tetrakis(perfluorophenyl) Aluminate, a Highly Efficient Activator for High-Temperature Ethylene-α-Olefin Copolymerization Reactions","authors":"Sean Bremer, Robert J. Bellair, Travis W. Scholtz, Todd D. Senecal* and Jerzy Klosin*, ","doi":"10.1021/acs.organomet.4c0026810.1021/acs.organomet.4c00268","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00268https://doi.org/10.1021/acs.organomet.4c00268","url":null,"abstract":"The new salt, [HNMe(C18H37)2][Al(C6F5)4], was prepared and was shown to be highly effective as an activator for Group IV precatalysts in high-temperature ethylene-1-octene copolymerization reactions. The performance of this activator closely mirrors that of the state-of-the-art activator borate-based analogue. Unlike the borate analogue, the aluminate activator reacts readily with water at ambient temperature, generating pentafluorobenzene, the only fluorine-containing product. Such a feature might be helpful when preparing polymers without any charged contaminants. Unlike some of the other aluminum compounds containing perfluorophenyl groups, [HNMe(C18H37)2][Al(C6F5)4] was found not to be impact-sensitive and is stable at ambient temperature for months. Detailed evaluation of this aluminate salt and several other aluminum alkyls/aryls (e.g., Al(C6F5)3(THF), Al(C6F5)3, AlEt3, and MMAO-3A) was carried out to evaluate their reactive chemistry and safety profiles.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.5,"publicationDate":"2024-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142517731","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

Mechanism Studies on the Chemical Stability of FIrpic, a Typical Blue Phosphorescent Emitter for Electroluminescence, in the Redox States 电致发光用典型蓝色磷光发光体 FIrpic 在氧化还原状态下的化学稳定性机理研究

IF 2.5 3区化学

Organometallics Pub Date : 2024-09-23 DOI: 10.1021/acs.organomet.4c0030310.1021/acs.organomet.4c00303

Weiqiang Wei, Luyan Huang, Zihan Wang, Ya Xu, Zhou Fang, Yan He, Lisheng Zhang and Huifang Li*,

{"title":"Mechanism Studies on the Chemical Stability of FIrpic, a Typical Blue Phosphorescent Emitter for Electroluminescence, in the Redox States","authors":"Weiqiang Wei, Luyan Huang, Zihan Wang, Ya Xu, Zhou Fang, Yan He, Lisheng Zhang and Huifang Li*, ","doi":"10.1021/acs.organomet.4c0030310.1021/acs.organomet.4c00303","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00303https://doi.org/10.1021/acs.organomet.4c00303","url":null,"abstract":"Iridium(III)bis[2-(4,6-difluorophenyl)pyridyl-N,C2′]picolinate (FIrpic) is a widely used light-blue phosphorescent material known for its favorable redox activity. However, the operational lifetime of FIrpic-based phosphorescent organic light-emitting diodes (PhOLEDs) remains unsatisfactory. To gain a deeper understanding of the chemical stability of FIrpic in various redox states, we explored its degradation mechanisms in the ground (S0), one-electron oxidized (Ox.), and one-electron reduced (Re.) states using theoretical methods. Density functional theory (DFT) static calculations, combined with atomic center density matrix propagation (ADMP) simulations at temperatures of 500, 600, and 700 K, revealed that the cleavage of the Ir–N1 bond is a crucial step in the chemical degradation process of FIrpic in both the ground and redox states. This bond breakage leads to a nonemissive five-coordinated trigonal bipyramidal intermediate. The degradation process is notably more facile in the redox states, particularly in the Re. Charge analysis indicates a decreasing trend in electronic delocalization between the LPN electron donor natural bond orbital (NBO) and the d*N–Ir(pic.) electron acceptor NBO, with the order S0 > Ox. > Re. Our findings provide a deeper insight into the degradation mechanisms of FIrpic under different redox conditions. This understanding is crucial for the design of more stable materials in FIrpic-based PhOLEDs.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.5,"publicationDate":"2024-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142437518","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