Organometallics最新文献

Experimental Studies of Reaction Mechanisms in Organometallic Chemistry and Catalysis

IF 2.5 3区化学

Organometallics Pub Date : 2024-12-23 DOI: 10.1021/acs.organomet.4c0047810.1021/acs.organomet.4c00478

Jennifer V. Obligacion*, Ana C. Albéniz and Mio Kondo,

引用次数: 0

Synthesis of Cyclic (Alkyl)(amino)carbene-Stabilized Copper–Iron Heterobimetallic Complexes and Their Application in Pyridine Hydroboration

IF 2.5 3区化学

Organometallics Pub Date : 2024-11-26 DOI: 10.1021/acs.organomet.4c0041310.1021/acs.organomet.4c00413

Ankita Sharma, Vikas Tiwari, Ritu Yadav, Bindusagar Das, Chinmoy Majumder, Ayantika Das, Tarak Karmakar* and Subrata Kundu*,

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N-Heterocyclic Carbene-Au(I)-Phosphine Complexes: Characterization, Theoretical Structure Analysis, and Anti-Cancer Properties

IF 2.5 3区化学

Organometallics Pub Date : 2024-11-26 DOI: 10.1021/acs.organomet.4c0040510.1021/acs.organomet.4c00405

Mohammad Reza Yousefshahi, Mahdi Cheraghi, Tahereh Ghasemi, Abdollah Neshat*, Vaclav Eigner, Michal Dusek, Mehrnaz Amjadi and Shiva Akbari-Birgani,

{"title":"N-Heterocyclic Carbene-Au(I)-Phosphine Complexes: Characterization, Theoretical Structure Analysis, and Anti-Cancer Properties","authors":"Mohammad Reza Yousefshahi, Mahdi Cheraghi, Tahereh Ghasemi, Abdollah Neshat*, Vaclav Eigner, Michal Dusek, Mehrnaz Amjadi and Shiva Akbari-Birgani, ","doi":"10.1021/acs.organomet.4c0040510.1021/acs.organomet.4c00405","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00405https://doi.org/10.1021/acs.organomet.4c00405","url":null,"abstract":"Derivatization of (NHC)Au–Cl with monodentate and bidentate phosphine donors, such as PPh2Py, PPh3, PCy3, and dppf, produced heteroleptic mononuclear and binuclear Au(I) complexes. The order of mixing reactants and the types of solvents used play crucial roles in obtaining a pure product. In the single-crystal X-ray diffraction analysis of complexes 1, 2, and 4, the Au(I) centers exhibited linear geometry. Advanced computational analysis of these complexes using density functional methods provided insights into the nature of electronic transitions, noncovalent interactions, and fragmental bonding contributions. Complexes 1–4 were selected for biological activity studies, and their in vitro cellular tests were conducted on the human cancerous breast cell line MCF-7, with bimetallic complex 4 showing the lowest IC50 value of 63 nM and demonstrating the highest inhibitory effect on cell proliferation.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"43 23","pages":"3031–3042 3031–3042"},"PeriodicalIF":2.5,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142850672","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

Insertions of Isocyanides in Diamidoamine Rhenium(III) Complexes

IF 2.5 3区化学

Organometallics Pub Date : 2024-11-26 DOI: 10.1021/acs.organomet.4c0033810.1021/acs.organomet.4c00338

Liana Pauly, Abdullahi K. Adegboyega, Caleb A. Brown, Damaris E. Pérez and Elon A. Ison*,

引用次数: 0

Exploring the Site Selectivity of Arene Oxidation in [(η5-C5Me5)Ir(η6-arene)](OTf)2 Complexes

IF 2.5 3区化学

Organometallics Pub Date : 2024-11-26 DOI: 10.1021/acs.organomet.4c0042110.1021/acs.organomet.4c00421

Carlota Odena, Marina Perez-Jimenez, Ronghui Lin and Paul J. Chirik*,

{"title":"Exploring the Site Selectivity of Arene Oxidation in [(η5-C5Me5)Ir(η6-arene)](OTf)2 Complexes","authors":"Carlota Odena, Marina Perez-Jimenez, Ronghui Lin and Paul J. Chirik*, ","doi":"10.1021/acs.organomet.4c0042110.1021/acs.organomet.4c00421","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00421https://doi.org/10.1021/acs.organomet.4c00421","url":null,"abstract":"The oxidation selectivity of the η6-arene ligand in a series of [(η5-C5Me5)Ir(η6-arene)](OTf)2 complexes to the corresponding [(η5-C5Me5)Ir(η5-phenoxo)](OTf) derivatives was studied as a complementary protocol to metal-catalyzed borylation-oxidation. A series of representative [(η5-C5Me5)Ir(η6-arene)](OTf)2 compounds was prepared with mono-, di-, and trisubstituted arenes as well as two examples with biphenyls to rationally explore the site selectivity of C(sp2)–H oxidation. The isolated organometallic arene complexes were treated with NaClO2 and formed the desired iridium η5-phenoxo products. While site-selective oxidation was observed for some compounds, most of the iridium complexes yielded a mixture of regioisomers. Regioselectivity was primarily determined by electronic factors, while sterics influenced sites that were electronically similar.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"43 23","pages":"3067–3073 3067–3073"},"PeriodicalIF":2.5,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142843700","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

Group 11 Bis(alumanyl)metallates

IF 2.5 3区化学

Organometallics Pub Date : 2024-11-26 DOI: 10.1021/acs.organomet.4c0046010.1021/acs.organomet.4c00460

Han-Ying Liu, Jakub Kenar, Samuel E. Neale, Marta Garofalo, Michael S. Hill*, Claire L. McMullin*, Mary F. Mahon* and Emma Richards,

{"title":"Group 11 Bis(alumanyl)metallates","authors":"Han-Ying Liu, Jakub Kenar, Samuel E. Neale, Marta Garofalo, Michael S. Hill*, Claire L. McMullin*, Mary F. Mahon* and Emma Richards, ","doi":"10.1021/acs.organomet.4c0046010.1021/acs.organomet.4c00460","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00460https://doi.org/10.1021/acs.organomet.4c00460","url":null,"abstract":"Reactions of the coinage metal (CM) cyanides, CuCN, AgCN, or K[Au(CN)2], with [{SiNDipp}AlK]2 ({SiNDipp} = {CH2SiMe2N(Dipp)}2; Dipp = 2,6-i-Pr2C6H3) result in KCN metathesis and a series of “alumina-Gilman” reagents, [({SiNDipp}Al)2CM]K (CM = Cu, Ag, or Au). The latter species may be isolated in both charge-separated, [({SiNDipp}Al)2CM]−[K(THF)6]+, or contact ion pair forms when crystallized in the presence or absence of THF. Computational analysis apportions a high degree of covalency to the CM–Al metal bonding and attribution of an aluminum oxidation state that is best represented as Al(II). This latter inference is supported by the experimental observation of THF activation, deduced to result from the competitive single electron reduction of the group 11 center during the synthesis of the bis(alumanyl)metalates. UV photolysis of [({SiNDipp}Al)2Ag]K provided a product of 2-fold Al(II) radical addition to benzene. This species is also synthesized by a modification of the reaction that gave rise to the initially identified cuprate metathesis product. The intermediacy of [{SiNDipp}Al•] radicals, which are proposed to add to benzene in a stepwise manner, is supported by the observation of in situ recorded EPR spectra, the simulated parameters of which have been assigned to the singly aluminated benzene product, [{SiNDipp}Al(C6H6)•].","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"43 23","pages":"3074–3086 3074–3086"},"PeriodicalIF":2.5,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.organomet.4c00460","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142843701","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}

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Prospects for the Use of Al/Mg Cocatalysts (AlknAlCl3–n + Alk2Mg) in the Polymerization of Olefins. Studies of the Interactions between the Activator Components

IF 2.5 3区化学

Organometallics Pub Date : 2024-11-20 DOI: 10.1021/acs.organomet.4c0036110.1021/acs.organomet.4c00361

Dmitry A. Kurmaev, Vladislav A. Tuskaev*, Svetlana C. Gagieva, Evgenii K. Golubev, Maria D. Evseeva, Tatiana V. Strelkova and Boris M. Bulychev,

{"title":"Prospects for the Use of Al/Mg Cocatalysts (AlknAlCl3–n + Alk2Mg) in the Polymerization of Olefins. Studies of the Interactions between the Activator Components","authors":"Dmitry A. Kurmaev, Vladislav A. Tuskaev*, Svetlana C. Gagieva, Evgenii K. Golubev, Maria D. Evseeva, Tatiana V. Strelkova and Boris M. Bulychev, ","doi":"10.1021/acs.organomet.4c0036110.1021/acs.organomet.4c00361","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00361https://doi.org/10.1021/acs.organomet.4c00361","url":null,"abstract":"Based on previously accumulated experimental material on the use of {nEt2AlCl + Bu2Mg} mixtures for the activation of Ti postmetallocene precatalysts for ethylene polymerization, an attempt is made to find the reason for the universal activating ability of such cocatalysts by analyzing the chemical processes occurring during the interaction of alkylaluminum chlorides and dibutylmagnesium. 1H and 27Al NMR spectroscopy data indicate that in nonsolvating media the formation of ionic products (with which earlier the unique activating ability of Al/Mg activators was associated) does not occur. The “true” Al/Mg cocatalysts are uncharged adducts of MgCl2 with alkylaluminum chlorides and/or trialkylaluminum. It was shown that all used Al/Mg cocatalyst compositions are capable of activating a model titanium dichloride complex with a saligenin ligand with varying efficiencies. The product of the ethylene polymerization is an ultrahigh molecular weight polymer (Mv from 1.1 to 5.1 × 106 Da); the latter is evidenced by the possibility of solid-phase processing of nascent polymer powders into high-strength, high-modulus tapes (breaking strength up to 2.4 GPa and elastic modulus up to 112 GPa).","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"43 23","pages":"3022–3030 3022–3030"},"PeriodicalIF":2.5,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142842771","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}

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Nickel(II) Complexes Bearing Electron Donating OR/OH Groups on a Tetradentate Ligand Scaffold for Photocatalytic Carbon Dioxide Reduction

IF 2.5 3区化学

Organometallics Pub Date : 2024-11-20 DOI: 10.1021/acs.organomet.4c0040810.1021/acs.organomet.4c00408

Sonya Y. Manafe, Gbolagade Olajide, Chance M. Boudreaux, Fengrui Qu, Logan M. Whitt, Patrick D. Pridemore, James Fletcher Hall, Tibor Szilvási* and Elizabeth T. Papish*,

{"title":"Nickel(II) Complexes Bearing Electron Donating OR/OH Groups on a Tetradentate Ligand Scaffold for Photocatalytic Carbon Dioxide Reduction","authors":"Sonya Y. Manafe, Gbolagade Olajide, Chance M. Boudreaux, Fengrui Qu, Logan M. Whitt, Patrick D. Pridemore, James Fletcher Hall, Tibor Szilvási* and Elizabeth T. Papish*, ","doi":"10.1021/acs.organomet.4c0040810.1021/acs.organomet.4c00408","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00408https://doi.org/10.1021/acs.organomet.4c00408","url":null,"abstract":"Nickel(II) complexes bearing tetradentate NCCN ligands composed of optionally protic pyridine and N-heterocyclic carbene (NHC) donors have been synthesized and used as catalysts for carbon dioxide reduction. These complexes were synthesized bearing OMe, OBn, or OH substituents on the pyridine rings and were characterized by 1H NMR, 13C NMR, UV–vis, IR, HR-MS, and single crystal X-ray diffraction. The OH substituent was partially deprotonated, as shown by the crystal structure. Electrochemical studies show that these nickel complexes undergo two electron reduction events prior to CO2 reduction. Catalytic current enhancement under CO2 relative to N2 is not observed under dry conditions, but the addition of proton sources leads to modest current enhancement (icat/ip < 2). Visible light driven photochemical CO2 reduction with a photosensitizer (Ir(ppy)3, where ppy = 2-phenylpyridine) and sacrificial electron and proton donors was studied, and formate is the major product with ∼10:1 formate to CO production. Electron donor groups (OMe, OBn, OH) do not enhance formate production (relative to the unsubstituted analogue), and CO production is only slightly enhanced. Overall with Ni(II), the tetradentate ligands are comparable to recently published pincer ligands for sensitized CO2 reduction, but pincer ligands offer a clear advantage in self-sensitized catalysis.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"43 23","pages":"3043–3053 3043–3053"},"PeriodicalIF":2.5,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142850564","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}

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Mixed Chloro-/Fluoroaryl Boranes as Lewis Acid Catalysts for C–O Bond Cleavage/Reduction

IF 2.5 3区化学

Organometallics Pub Date : 2024-11-20 DOI: 10.1021/acs.organomet.4c0042010.1021/acs.organomet.4c00420

Nathan E. DeSousa, and , Michel R. Gagné*,

{"title":"Mixed Chloro-/Fluoroaryl Boranes as Lewis Acid Catalysts for C–O Bond Cleavage/Reduction","authors":"Nathan E. DeSousa,  and , Michel R. Gagné*, ","doi":"10.1021/acs.organomet.4c0042010.1021/acs.organomet.4c00420","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00420https://doi.org/10.1021/acs.organomet.4c00420","url":null,"abstract":"A simplified one-pot procedure for the synthesis of a useful class of mixed chloro-/fluoroaryl boranes following the formula B(C6Cl5)n(C6F5)3–n is reported. Standard organolithium and Grignard reagents are utilized, and intermediate arylzinc or arylcopper reagents are not required. With regard to their applications to C–O cleavage reactions, the increased steric bulk of having ortho-chlorine enhances the catalyst tolerance of water, allowing for C–O deoxygenations under atmospheric conditions. As the degree of chlorination increases, the reactivity of the borane catalyst decreases with B(C6Cl5)(C6F5)2 being the most active of the boranes studied. This mono-C6Cl5 borane was able to cleave or reduce the C–O bond of ethers, carbonyls, and sugars under benchtop (open air) conditions. B(C6Cl5)(C6F5)2 thus demonstrates a favorable balance of water tolerance and preserved reactivity relative to that of BCF itself.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"43 23","pages":"3062–3066 3062–3066"},"PeriodicalIF":2.5,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142850565","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

Amino Imidazoline-2-imine-Chelated Triel Carbenoids as Ligands for Ruthenium Complexes: DFT Studies on Their Activity as Potential Olefin Metathesis Catalysts

IF 2.5 3区化学

Organometallics Pub Date : 2024-11-19 DOI: 10.1021/acs.organomet.4c0025610.1021/acs.organomet.4c00256

Tymoteusz Basak*, and , Bartosz Trzaskowski*,

引用次数: 0