Organometallics最新文献_第5页

Impressions of the Development of the Open-Shell Chemistry and Multiple Bonding in Heavier Main-Group Species 重主基团中开壳化学和多键发展的印象

IF 2.4 3区化学

Organometallics Pub Date : 2026-08-24 Epub Date: 2026-08-10 DOI: 10.1021/acs.organomet.6c00213

Philip P. Power, Cary R. Stennett

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Shelf-Stable Bis(perfluoroaryl)nickel(II) Complexes for Organometallic Synthesis and Catalysis 货架稳定的双（全氟芳基）镍（II）配合物，用于有机金属合成和催化

IF 2.4 3区化学

Organometallics Pub Date : 2026-08-24 Epub Date: 2026-06-22 DOI: 10.1021/acs.organomet.6c00134

Nana Kim, Aimee L. Bangerter, Yeongyu Hwang, Anne K. Ravn, Taylor M. Keller, Sloan Ayers, Amy A. Sarjeant, Milan Gembicky, Jake Bailey, Erika Samolova, Zachary J. Garlets, Job J. C. Struijs, Matthew V. Joannou, Omar Apolinar, Sean P. Dunphy, Joshua S. Figueroa, Steven R. Wisniewski, Keary M. Engle

{"title":"Shelf-Stable Bis(perfluoroaryl)nickel(II) Complexes for Organometallic Synthesis and Catalysis","authors":"Nana Kim, Aimee L. Bangerter, Yeongyu Hwang, Anne K. Ravn, Taylor M. Keller, Sloan Ayers, Amy A. Sarjeant, Milan Gembicky, Jake Bailey, Erika Samolova, Zachary J. Garlets, Job J. C. Struijs, Matthew V. Joannou, Omar Apolinar, Sean P. Dunphy, Joshua S. Figueroa, Steven R. Wisniewski, Keary M. Engle","doi":"10.1021/acs.organomet.6c00134","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00134","url":null,"abstract":"We describe two bis(perfluoroaryl)nickel(II) complexes,Ni(C6F5)2(NCPh)2 and [NBu4]2[{Ni(C6F5)2(μ–OH)2}2], as bench-stable, broadly soluble, and readilycoordinating Ni(II) sources for applications in organometallic synthesisand catalysis. Their catalytic competence is demonstrated across representativetransformations, including Suzuki–Miyaura coupling, Buchwald–Hartwigamination, Miyaura borylation, and recently developed alkene difunctionalizationreactions, with performance comparable to or exceeding that of conventionalNi sources. The presumed activation pathway via reductive eliminationof decafluorobiphenyl offers a benign route, minimizing off-cyclespecies formation.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 16","pages":"1920–1927"},"PeriodicalIF":2.4,"publicationDate":"2026-08-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148810342","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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Flash Communication: A Dithiolene-Based Hexathiadisila[4.4.4]propellene 闪光通信：一种基于二硫代烯的hexathadiisila[4.4.4]推进剂

IF 2.4 3区化学

Organometallics Pub Date : 2026-08-24 Epub Date: 2026-08-12 DOI: 10.1021/acs.organomet.6c00227

John C. Johnson, Yuzhong Wang, Claire Buck, Pingrong Wei, Mitchell E. Lahm, Henry F. Schaefer, III, Gregory H. Robinson

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Computational Study of the Palladium-Catalyzed Tandem Transformation of Phosphinyl Allene to Benzo[b]phosphole Oxide: Key Roles of the Palladacycle Structure and Ancillary Ligands 钯催化磷酸基烯串联转化为苯并[b]氧化膦孔的计算研究：钯环结构和辅助配体的关键作用

IF 2.4 3区化学

Organometallics Pub Date : 2026-08-24 Epub Date: 2026-08-06 DOI: 10.1021/acs.organomet.6c00192

Bowen Zhang

{"title":"Computational Study of the Palladium-Catalyzed Tandem Transformation of Phosphinyl Allene to Benzo[b]phosphole Oxide: Key Roles of the Palladacycle Structure and Ancillary Ligands","authors":"Bowen Zhang","doi":"10.1021/acs.organomet.6c00192","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00192","url":null,"abstract":"The ortho selectivity of C–Hactivationin the palladium-catalyzed annulation of phosphinyl allenes to formbenzo[b]phosphole oxides has previously been attributedto coordinative assistance from the adjacent P═O moiety. Inthis study, comprehensive structural and energetic analyses reveala different mechanistic origin. The observed ortho C–H activation is governed primarily by the preferred six-memberedtwisted-boat conformation of the palladacyclic transition state. Thepresumed P═O···Pd coordination does not exerta directing effect; instead, it distorts the favorable palladacyclicgeometry and raises the transition-state energy to a prohibitive level,making its involvement in C–H activation infeasible. A closerinspection of the elementary steps in this cascade reaction showsthat ancillary ligands modulate two key processes in opposite directions:they elevate the oxidative addition barrier while markedly stabilizingthe C–H activation transition state. As a result, the overallrate-limiting step depends sensitively on the electron count (14e– or 16e–) of the active Pd(0) species, as well as the identity of the ancillaryligand. Collectively, these findings support a strain- and ligand-controlledmechanism rather than the previously assumed heteroatom-directed C–Hactivation model, providing new insights into palladium-catalyzedallene annulation and heterocycle construction.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 16","pages":"1998–2011"},"PeriodicalIF":2.4,"publicationDate":"2026-08-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148810185","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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Molecular Conductances of Styryl Ruthenium and Divinylphenylene-Bridged Diruthenium Complexes with Thioanisyl Anchor Groups 含硫氨酰基锚基的苯乙烯基钌和二乙烯基苯乙烯桥联二钌配合物的分子电导率

IF 2.4 3区化学

Organometallics Pub Date : 2026-08-24 Epub Date: 2026-06-24 DOI: 10.1021/acs.organomet.6c00111

Viktoria Ebel, Moritz Nau, Michael Linseis, Rainer F. Winter

{"title":"Molecular Conductances of Styryl Ruthenium and Divinylphenylene-Bridged Diruthenium Complexes with Thioanisyl Anchor Groups","authors":"Viktoria Ebel, Moritz Nau, Michael Linseis, Rainer F. Winter","doi":"10.1021/acs.organomet.6c00111","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00111","url":null,"abstract":"We report the synthesis of new mononuclear styryl anddinucleardivinylphenylene-bridged diruthenium complexes, terminated on bothends with thiomethyl (−SMe) substituents at the styryl andthe bidentately coordinating benzoate or β-acetylphenolate chelateligands. Robust binding of the SMe functionalities to surface atomsof nanoscale gold electrodes enables the modified complex moleculesto establish nanojunctions in scanning tunneling microscopy break-junctionexperiments. Ten of the 13 complexes provided defined molecular conductancefeatures that could be evaluated. Complexes with β-ketoenolateligands proved to be somewhat better conductors than those with benzoateligands, and the dinuclear complexes, despite their considerably largermolecular lengths, proved to be more conductive than the mononuclearones. While the molecular conductances of the present complexes areat the low end of those with rigid-rod fully π-conjugated ethynylarylenebackbones and linkages, their modular design makes this type of complexa versatile testbeds for probing the impact of every constituent onthe molecular conductances of such metal complex-based wires.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 16","pages":"1888–1904"},"PeriodicalIF":2.4,"publicationDate":"2026-08-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148810345","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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Flash Communication: A Lewis Acidity-Diminished, Stable Diborylethyne 闪光通信：路易斯酸减少，稳定二乙基乙烯

IF 2.4 3区化学

Organometallics Pub Date : 2026-08-24 Epub Date: 2026-08-04 DOI: 10.1021/acs.organomet.6c00230

Yusaku Nishihara, Kenjiro Abe, Jialun Li, Masaaki Nakamoto, Takuya Michiyuki, Takumi Tsushima, Hiroto Yoshida

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Anticancer Active Cyclometalated Iridium(III) Complexes Bearing Substituted 1,2,4-Triazine: Biomolecular Interactions and Gene Expression Studies in Drosophila melanogaster 含取代1,2,4-三嗪的抗癌活性环金属化铱（III）配合物：黑腹果蝇的生物分子相互作用和基因表达研究

IF 2.4 3区化学

Organometallics Pub Date : 2026-08-24 Epub Date: 2026-08-08 DOI: 10.1021/acs.organomet.6c00136

Madhusmita Jadab, Subhasmita Bhal, Chanakya Nath Kundu, Atanu Sahoo, Manas Kumar Santra, Rout George Kerry, Sahadev Barik, Jagadish Kumar, Sanatan Majhi, Satyanarayan Pal

{"title":"Anticancer Active Cyclometalated Iridium(III) Complexes Bearing Substituted 1,2,4-Triazine: Biomolecular Interactions and Gene Expression Studies in Drosophila melanogaster","authors":"Madhusmita Jadab, Subhasmita Bhal, Chanakya Nath Kundu, Atanu Sahoo, Manas Kumar Santra, Rout George Kerry, Sahadev Barik, Jagadish Kumar, Sanatan Majhi, Satyanarayan Pal","doi":"10.1021/acs.organomet.6c00136","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00136","url":null,"abstract":"Cationic bis-heteroleptic Ir(III) complexes (Ir1–Ir3) bearing 3-(2-pyridyl)-5,6-diphenyl-1,2,4-triazine (pdpt) as an ancillary ligand were synthesized using three different cyclometallatingligands. Structural characterization by FT-IR, ESI-MS and 1D/2D NMRconfirmed the formation of the complexes, while the molecular structureof Ir1 was elucidated from single-crystal X-ray diffraction.Photophysical studies revealed that all complexes exhibited red-lightemission under UV light. The complexes demonstrated high kinetic stabilityunder biologically relevant conditions. Biomolecular studies in cell-freeconditions showed strong binding affinities toward DNA and BSA, with Ir1 exhibiting the highest interaction. Cytotoxicity evaluationagainst MCF-7, MDA-MB-231, and A549 cancer cell lines revealed significantanticancer activity. Among the three complexes, Ir2 displayedthe highest cytotoxicity, whereas Ir3 showed the leastpotency. The exploration of selectivity toward MCF10A disclosed theoptimal balance between anticancer efficacy and selectivity of Ir1. The in vitro noncytotoxicity of these complexes againstHEK-293 cells further highlighted the superior activity relative tothe conventional Pt-based cancer drugs. The anticancer efficacy ofcomplexes was examined in treated MCF-7 cancer cells through DAPInuclear staining assays and arrest of the cell cycle at the G0/G1 phase, analyzed from flow cytometry. Finally,in vivo toxicity screening in Drosophila melanogaster connected gene expression changes to developmental abnormalities,confirming Ir2 as the most cytotoxic complex.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 16","pages":"1928–1946"},"PeriodicalIF":2.4,"publicationDate":"2026-08-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148810054","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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A Parallelogram Tetranickel Complex with a Short Ni–Ni Bond Supported by a Pentadentate N-Ligand 一种由五齿n配体支撑的短Ni-Ni键的平行四边形四镍配合物

IF 2.4 3区化学

Organometallics Pub Date : 2026-08-24 Epub Date: 2026-08-10 DOI: 10.1021/acs.organomet.6c00209

Xiaoqing Xin, Junqing Hou, Shanshan Wang, Qian Zhang, Lun Luo, Ruogu Qi

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Dual Active Forms of Milstein’s Catalyst for Ester Hydrogenation 酯加氢Milstein催化剂的双活性形式

IF 2.4 3区化学

Organometallics Pub Date : 2026-08-24 Epub Date: 2026-08-05 DOI: 10.1021/acs.organomet.6c00183

Haitian Ye, Jason M. Keith, Anthony R. Chianese

{"title":"Dual Active Forms of Milstein’s Catalyst for Ester Hydrogenation","authors":"Haitian Ye, Jason M. Keith, Anthony R. Chianese","doi":"10.1021/acs.organomet.6c00183","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00183","url":null,"abstract":"In this article,we report that Milstein’s ruthenium-pincercatalyst for ester hydrogenation, previously shown to convert to ahighly active form through release of ethane, is also moderately activein its original form prior to ethane release, provided an alcoholcocatalyst is present. We describe a detailed experimental and computationalstudy of ester hydrogenation catalyzed by the catalyst’s originalform. The reaction rate is first-order in ester and ruthenium catalyst,zero-order in hydrogen, and exhibits a saturation dependence on theconcentration of the product alcohol. We establish that an equilibriumbetween two potential resting states, a dihydride complex and a hydridoalkoxidecomplex, is shifted nearly completely toward the dihydride under catalyticallyrelevant conditions. We report a thorough computational analysis ofthe mechanism, which is consistent with the observed kinetics andcatalyst resting speciation. In the minimum-energy pathway, esterreduction proceeds through dechelation of the pincer’s diethylaminogroup, and the CH2 linkers of the pincer ligand are notinvolved in catalytic turnover. Two alternative pathways involvingH/OR metathesis or pincer ligand dearomatization proceed with free-energybarriers that are 1.1 and 1.5 kcal/mol higher, respectively; thesecomputationally identified pathways are not fully consistent withthe kinetic data.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 16","pages":"1983–1997"},"PeriodicalIF":2.4,"publicationDate":"2026-08-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148810213","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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Synthesis, Reactivity, and Photophysical Properties of Cyclometalated 6-Arylphenanthridines 环金属化6-芳基菲的合成、反应性及光物理性质

IF 2.4 3区化学

Organometallics Pub Date : 2026-08-24 Epub Date: 2026-08-14 DOI: 10.1021/acs.organomet.6c00253

Petr Harmach, Timothée Cadart, Ivana Císařová, Martin Kotora, Thomas Strassner, Petr Štepnička

{"title":"Synthesis, Reactivity, and Photophysical Properties of Cyclometalated 6-Arylphenanthridines","authors":"Petr Harmach, Timothée Cadart, Ivana Císařová, Martin Kotora, Thomas Strassner, Petr Štepnička","doi":"10.1021/acs.organomet.6c00253","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00253","url":null,"abstract":"Cyclometalation reactions proceeding by a concerted metalation-deprotonationmechanism are recognized as efficient routes toward new organometalliccompounds. Using this approach, we reacted 6-(4-tolyl)phenanthridine(1) and 6-(4-(trifluoromethyl)phenyl)phenanthridine (2) with [(η5-C5Me5)MCl2]2 (M = Rh and Ir) in the presence of sodium acetateand obtained the respective cyclometalated products [(η5-C5Me5)MCl(1–H)]and [(η5-C5Me5)MCl(2–H)] in varying yields (20–80%). An unexpected productof 2-fold C–H bond activation [Rh(OAc)(1–H)2] (3) was also isolated. The compounds were characterizedby NMR spectroscopy and mass spectrometry, and the structures of therepresentative complexes were determined by single-crystal X-ray diffractionanalysis. In addition, the photophysical properties of the cyclometalatedcompounds were studied using UV–vis and luminescence spectroscopy,and the data were rationalized by DFT calculations. The reaction of[(η5-C5Me5)RhCl(1–H)] with tolane in the presence of a Cu(II) salt as an oxidantafforded 9-methyl-6,7-diphenylisoquinolino[2,1-f]phenanthridin-5-iumtetrafluoroborate, an annulated product, which suggested that thecyclometalated complexes are plausible intermediates of such annulationreactions.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 16","pages":"2051–2058"},"PeriodicalIF":2.4,"publicationDate":"2026-08-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148810446","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