Organometallics最新文献

{"title":"A BN-Isostere of a Porous Organic Polymer Using Azabora-Spirobifluorenes","authors":"Isabel W. He,&nbsp;Kang Yuan,&nbsp;Arnaud Osi,&nbsp;Dominic Taylor,&nbsp;Gary S. Nichol,&nbsp;Neil B. McKeown,&nbsp;Michael J. Ingleson","doi":"10.1021/acs.organomet.6c00284","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00284","url":null,"abstract":"<p>Porous organic polymersthat can be processed using organic solventsare attractive materials for a range of applications. Switching aCC unit for an isoelectronic BN unit is a powerful method to modulatethe key properties of organic polymers; however, this approach isunderexplored in the field of soluble porous organic polymers. Toaccess isostructural CC/BN porous organic polymers, the synthesisof azabora-spirobifluorenes (BN-SBF) functionalized with methoxy/bromogroups was developed. While the use of 9-bromo-9-borafluorene (<strong>1</strong>) in pyridine-directed electrophilic borylation enabled thesynthesis of a dimethoxy-substituted BN-SBF, this method could notbe extended to access a tetramethoxy-BN-SBF derivative. The lattercompound, while accessible via a lithiation/transmetalation route,was incompatible with various ether cleavage protocols. A BN-SBF-containingpolymer instead was synthesized using a dibromo-functionalized BN-SBFmonomer, which also could be synthesized via pyridine-directed electrophilicborylation using compound <strong>1</strong>. The BN-SBF-based polymerproved to have comparable porosity to its CC analogue; however, itand the CC analogue did not form robust free-standing membranes. Nevertheless,this work highlights the feasibility of accessing a BN isostere ofan established solution-processable porous organic polymer.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 20","pages":"2414–2419"},"PeriodicalIF":2.4,"publicationDate":"2026-10-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149282037","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":"Issues in the Electrochemical Dehydrogenation of Secondary Amines","authors":"Ignacio Camarero Temiño,&nbsp;Mikhaila D. Ritz,&nbsp;William D. Jones","doi":"10.1021/acs.organomet.6c00278","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00278","url":null,"abstract":"<p>Herein, we report mechanistic studies on the ruthenium-catalyzeddehydrogenation of secondary amines using 2,6-dimethoxybenzoquinoneas an electrochemically regenerable mediator. The Shvo catalyst [(C₅Ph₄O)RuH]₂ operates at 90 °C ata potential of +0.4 V to dehydrogenate the amine to the imine at theanode. Hydrogen gas is generated at the cathode. Issues such as protonationof the amine are identified and circumvented by using lutidine asa proton-transfer base.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 20","pages":"2491–2497"},"PeriodicalIF":2.4,"publicationDate":"2026-10-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149282052","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":"Flash Communication: Lithium 1,4-Diazine Triple Ion Radical Complexes─Structural Isolation and Trends in Spin Delocalization","authors":"Fahmida Islam,&nbsp;George D. Tisdale,&nbsp;Frank R. Fronczek,&nbsp;Clifton L. Wagner","doi":"10.1021/acs.organomet.6c00266","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00266","url":null,"abstract":"<p>A series of dilithium1,4-diazine radical anion complexesweresynthesized as analogs to alkali triple ion radical complexes. Thesolid-state structures display bond metrics consistent with single-electronreduction of the bridged diazine. EPR analysis shows diazine-localizedspin density with a small contribution to the coordinated lithiumatoms in the quinoxaline radical anion (<strong>2</strong>), while thephenazine radical anion (<strong>3</strong>) displays no measurable lithiumhyperfine coupling, indicating negligible lithium contribution tothe spin distribution.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 20","pages":"2404–2408"},"PeriodicalIF":2.4,"publicationDate":"2026-10-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149282011","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":"Cyclobutadiene (and Its Higher Homologues) Complexes of the s-, p-, d-, and f-Block Elements","authors":"Vladimir Ya. Lee,&nbsp;Valentine P. Ananikov,&nbsp;Mikhail P. Egorov,&nbsp;Mikhail A. Syroeshkin","doi":"10.1021/acs.organomet.6c00214","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00214","url":null,"abstract":"<p>Square-planar triplet cyclobutadieneis intrinsicallyunstable,given its four π-electron configuration leading to unavoidableantiaromatic destabilization. One effective way to stabilize cyclobutadieneis through its incorporation into the coordination sphere of an elementcapable of electron donation. Metals (main group metals, transitionmetals, lanthanides, and actinides) are most frequently used as electron-donatingelements, although recently, it was established that the main groupelements may also serve as capping donors in cyclobutadiene complexes.The recent advances in the chemistry of the cyclobutadiene complexesof the s-, p-, d-, and f-block elements are briefly summarized inthis review.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 20","pages":"2375–2403"},"PeriodicalIF":2.4,"publicationDate":"2026-10-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149282032","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 Aryl Substituents in Pyridyl-Imidazopyridine Ligands on the Aggregation-Induced Emission of Organoiridium(III) Complexes: Implications of 3MLCT and 3ILCT Excited States","authors":"Monosh Rabha,&nbsp;Khanindram Baruah,&nbsp;Deikrisha Lyngdoh Lyngkhoi,&nbsp;Themmila Khamrang,&nbsp;Rakshantha Srithar,&nbsp;Susnata Pramanik,&nbsp;Snehadrinarayan Khatua","doi":"10.1021/acs.organomet.6c00217","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00217","url":null,"abstract":"<p>In this study, three cyclometalated iridium(III) complexes, <strong>1[PF</strong>_{<strong>6</strong>}<strong>], 2[PF</strong>_{<strong>6</strong>}<strong>]</strong>, and <strong>3[PF</strong>_{<strong>6</strong>}<strong>]</strong>, incorporating 3-aryl-substituted pyridyl imidazopyridineligands, were synthesized and characterized using spectroscopic andsingle-crystal X-ray diffraction analysis. Photophysical studies revealedthat the complexes <strong>1[PF</strong>_{<strong>6</strong>}<strong>]</strong> and <strong>2[PF</strong>_{<strong>6</strong>}<strong>]</strong> exhibited weak emission in acetonitrile but displayed pronouncedaggregation-induced emission (AIE) in water-rich mixtures, whereas <strong>3[PF</strong>_{<strong>6</strong>}<strong>]</strong> remained nonemissiveboth in solution and in the aggregation state. Crystallographic analysisand DFT-optimized structure showed that the nearly parallel arrangementof the anthracenyl and 2-phenylpyridine moieties restricts intramolecularmotion in <strong>3[PF</strong>_{<strong>6</strong>}<strong>]</strong> both in solution and aggregated state but does not show emissiondue to the population of a dark ³LC state. In contrast,the phenyl and naphthyl substituents in <strong>1[PF</strong>_{<strong>6</strong>}<strong>]</strong> and <strong>2[PF</strong>_{<strong>6</strong>}<strong>]</strong> undergo greater intramolecular motion in dilutesolution, while their restriction upon aggregation promotes a strongemission enhancement. Additionally, biological response analysis ofcomplexes <strong>1[PF</strong>_{<strong>6</strong>}<strong>]</strong> and <strong>2[PF</strong>_{<strong>6</strong>}<strong>]</strong> demonstratedlow cytotoxicity toward HeLa cells and the complexes were successfullyemployed for live-cell imaging studies. This work provides new insightsinto an unusual fluorescence-quenching mechanism in cyclometalatediridium(III) complexes and offers valuable guidelines for the rationaldesign of luminescent iridium-based materials.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 20","pages":"2454–2467"},"PeriodicalIF":2.4,"publicationDate":"2026-10-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149282141","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":"Flash Communication: Catching Platinum Red-Handed: Exhaustive Ligand Redistribution at a Tucked-In Iron Complex","authors":"Alexandre M. D. J. Almeida,&nbsp;Logan J. Taylor,&nbsp;A. Dina Dilinaer,&nbsp;Marcus W. Drover","doi":"10.1021/acs.organomet.6c00324","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00324","url":null,"abstract":"<p>Transmetalation conventionally entails the transfer ofa singleligand (e.g., aryl, hydride, or alkyl) between two centers. Herein,we demonstrate a 3d-to-5d metal-to-metal transmetalation in whichthe iron center of an organometallic fulvene complex is formally replacedby platinum, ultimately leaving an iron fragment devoid of ancillaryligands. Representative intermediates, including two trimetallic {Fe₂Pt} complexes, were characterized by single-crystal X-raydiffraction, providing direct insight into the sequence of metal–carbonbond formation and ligand reorganization underlying this transmetalation.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 20","pages":"2436–2439"},"PeriodicalIF":2.4,"publicationDate":"2026-10-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149282046","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":"Iridium-Catalyzed α-C(sp3)–H Borylation of Trialkylhydrosilanes","authors":"Takeru Torigoe,&nbsp;Shunta Yamamoto,&nbsp;Toshimichi Ohmura","doi":"10.1021/acs.organomet.6c00303","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00303","url":null,"abstract":"<p>Itis known that trialkylhydrosilanes undergo either Si–Hor γ-C–H borylation in the iridium-catalyzed reactionwith bis(pinacolato)diboron. We developed α-C–H borylationas a new iridium-catalyzed reaction of trialkylhydrosilanes. The keyto changing the reaction mode was the use of 2,2′-bipyridinesbearing a methyl group at the 5- or 6-position as ligands for theiridium catalyst. This reaction allows direct access to syntheticallyuseful α-borylated hydrosilanes from readily available trialkylhydrosilanes.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 20","pages":"2425–2429"},"PeriodicalIF":2.4,"publicationDate":"2026-10-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149282157","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":"Flash Communication: Ni Nanoparticle Catalyst Supported on Organosilica Material Containing Ordered Triene Coordination Sites for the Suzuki–Miyaura Cross-Coupling Reaction","authors":"Yuki Inagaki,&nbsp;Shinji Tanaka,&nbsp;Masaru Yoshida,&nbsp;Koji Kimoto,&nbsp;Shinji Inagaki,&nbsp;Hajime Kawanami,&nbsp;Yumiko Nakajima","doi":"10.1021/acs.organomet.6c00288","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00288","url":null,"abstract":"<p>Nickelnanoparticles with a uniform diameter of ca. 2 nm were synthesizedsimply by mixing a Ni(0) precursor and a crystalline organosilicasupport <strong>triene-SiO</strong>_{<strong>2</strong>}<strong>-TMS</strong>, which possesses ordered triene coordination sites within the siloxanenetwork. The Ni nanoparticles catalyzed the Suzuki–Miyauracross-coupling of aryl halides without addition of exogenous ligands.A series of functional groups was compatible in the system. The catalystretained its activity even when handled under air.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 20","pages":"2420–2424"},"PeriodicalIF":2.4,"publicationDate":"2026-10-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149282158","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":"A Nickel Pre-Catalyst for the O-Arylation of Primary, Secondary, and Tertiary Alcohols with (Hetero)aryl Chlorides","authors":"Emily C. Jackson,&nbsp;Erika M. H. Elliott,&nbsp;Kathleen M. Morrison,&nbsp;Peter L. Fox,&nbsp;Katherine N. Robertson,&nbsp;Patrick L. DeRoy,&nbsp;Mark Stradiotto","doi":"10.1021/acs.organomet.6c00313","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00313","url":null,"abstract":"<p>While base metal-catalyzed cross-couplingsof alcohols and (hetero)arylchlorides have emerged over the past decade, the development of asingle pre-catalyst capable of promoting such transformations spanningall of primary, secondary, and tertiary (aliphatic) alcohols remainsan enduring challenge. Herein we disclose the easily prepared, air-stable4-cyanophenyl pre-catalyst (<strong>L2</strong>)Ni(4-CN-Ph)Cl (<strong>L2</strong> = CgPhen-DalPhos), which is shown to be capable of promoting, withuseful reaction scope, the C–O cross-coupling of all such alcoholclasses with (hetero)aryl chlorides.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 19","pages":"2266–2270"},"PeriodicalIF":2.4,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173572","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":"Reactions of [Ru3(CO)10(μ-dppf)] with Internal Alkynes: A Fine Balance between C–H and P–C Oxidative-Addition to the Triruthenium Center","authors":"Md. Arshad H. Chowdhury,&nbsp;Shahin A. Begum,&nbsp;Jagodish C. Sarker,&nbsp;Md. Monir Hossain,&nbsp;Subas Rajbangshi,&nbsp;Vladimir N. Nesterov,&nbsp;Graeme Hogarth,&nbsp;Shariff E. Kabir","doi":"10.1021/acs.organomet.6c00224","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00224","url":null,"abstract":"<p>The reactivity of[Ru₃(CO)₁₀(μ-dppf)](<strong>1</strong>) [dppf = 1,1′-bis(diphenylphosphino)ferrocene]toward internal alkynes, RC≡CR (<em>R</em> = Et, Ph,CO₂Me, CO₂Et), has been explored. Isolated productsvary with the nature of the alkyne substituent and differ from thosegenerated with related diphosphine-stabilized triruthenium clusters.In all products, one or two equivalents of alkyne are incorporatedand three or four carbonyls are lost. With hex-3-yne, the allenylcluster [Ru₃(CO)₇(μ-H)(μ-dppf)(μ₃-η¹:η²:η²-MeCHC≡CEt)] (<strong>2</strong>) results via aliphatic C–Hbond activation of one of the ethyl groups. With diphenylacetylene,the major product is [Ru₃(CO)₆(μ-H){μ-Ph₂P(C₅H₃)Fe(C₅H₄)PPh₂}(μ₃-η¹:η¹:η²-PhC₂Ph)] (<strong>3</strong>)which contains a capping alkyne ligand and a metalated dppf ligand,formed via C–H activation of one of the cyclopentadienyl rings.Metalation results in formation of a dative Fe–Ru bond. Withactivated alkynes (RCO₂)C₂(CO₂R)(<em>R</em> = Me, Et), alkyne coupling occurs to afford theopen 52-electron clusters [Ru₃(μ-CO)(CO)₆(μ-PPh₂){μ-η¹:κ¹-Ph₂P(C₅H₄)Fe(C₅H₄)}{μ₃-η¹:η²:η²:κ¹-C₄(CO₂R)₄}] (<strong>4–5</strong>). The later containbridging phosphido (PPh₂) and chelating Ph₂PFe(C₅H₄)₂ ligands, formed via a previouslyunreported P–C bond cleavage of the coordinated dppf ligand.All four new clusters have been characterized by single-crystal X-raydiffraction studies. We discuss likely reaction pathways and why thesetransformations differ so much as a function of the appended diphosphineligand.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 19","pages":"2271–2278"},"PeriodicalIF":2.4,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173951","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}