Organometallics最新文献

{"title":"","authors":"Christine M. Thomas*, Tianze Song and Joshua E. Goldberger*, ","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 14","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":2.5,"publicationDate":"2025-07-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.organomet.5c00222","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144712575","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":"","authors":"Víctor Martínez-Agramunt, Lucas H. R. Passos, Dmitry G. Gusev, Eduardo Peris and Eduardo N. dos Santos*, ","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 14","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":2.5,"publicationDate":"2025-07-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.organomet.5c00094","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144712578","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":"","authors":"Harish Parihar, Pooja Yadav and Natesan Thirupathi*, ","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 14","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":2.5,"publicationDate":"2025-07-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.organomet.5c00056","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144712581","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":"","authors":"Masaru Tanaka, Shota Kamiyama, Kei Ota and Norio Nakata*, ","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 14","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":2.5,"publicationDate":"2025-07-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.organomet.5c00200","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144712589","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":"Syntheses, Structures, Reactivity, and Catalytic Applications of Enantiopure Rhenium-Containing P-Stereogenic Phosphonium Salts, Phosphines, Phosphine Boranes, and Phosphine Oxides","authors":"Dante A. Castillo Molina,&nbsp;Florian O. Seidel,&nbsp;Kriti Pathak,&nbsp;Stephen A. Williams,&nbsp;Frank Hampel and John A. Gladysz*,&nbsp;","doi":"10.1021/acs.organomet.5c00171","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00171","url":null,"abstract":"<p >Easily accessed enantiopure (η⁵-C₅H₅)Re(NO)(PPh₃)(CH₃) is treated with Ph₃C⁺ PF₆^– (−78 °C) to generate the methylidene cation [(η⁵-C₅H₅)Re(NO)(PPh₃)(=CH₂)]⁺ and then racemic chiral secondary phosphines PHXX′ (<b>4</b>; X/X′ = <b>a</b>, <i>t</i>Bu/Ph; <b>b</b>, Cy/Ph; <b>c</b>, <i>t</i>Bu/Cy; <b>d</b>, CH₃/Ph; <b>e</b>, 2-furyl/Ph; <b>f</b>, α-naph/Ph; <b>g</b>, β-naph/Ph) to give the phosphonium salts (<i>S</i>_Re<i>R</i>_P)- and (<i>S</i>_Re<i>S</i>_P)-[(η⁵-C₅H₅)Re(NO)(PPh₃)(CH₂PHXX’)]⁺ PF₆^– (<b>2</b>·H⁺) as mixtures of Re, P-diastereomers that are usually separable (<b>a</b>,<b>b</b>,<b>c</b>,<b>f</b>,<b>g</b>). Treatment of <b>2a</b>-<b>g</b>·H⁺ with <i>t</i>BuOK generates the phosphines <b>2a</b>-<b>g</b>, which are variously isolated (<b>2f</b>,<b>g</b>), treated with BH₃·S(CH₃)₂ to give <b>2a</b>-<b>e</b>·BH₃, or oxidized (O₂ or PhIO) to give <b>2a</b>-<b>c</b>·O. Oxidations are also effected with <b>2a</b>,<b>c</b> that has been generated from <b>2a</b>,<b>c</b>·BH₃ and pyrrolidine. For the diastereomerically pure complexes in the <b>a</b>-<b>c</b> series, configurations have been assigned crystallographically, and the Ph₃P–Re–CH₂–P−X conformations were analyzed in detail. In an unusual but precedented phenomenon, the diastereomers of <b>2a</b>·H⁺ PF₆^– cocrystallize. <b>2f</b>,<b>g</b> catalyze highly enantioselective intramolecular Morita–Baylis–Hillman cyclizations of R(CO)CH═CHCH₂CH₂CHO (R═Ph, S<i>i</i>Pr), and (<i>S</i>_Re<i>S</i>_P)-<b>2b</b> (2.4 mol %) and [Pd(allyl)Cl]₂ (1.2 mol % based upon “Pd atoms”) give a catalyst for the allylic alkylation of racemic 3-(acetoxy)cyclohexene that furthermore effects a kinetic resolution of the educt (<i>s</i> = 15.0).</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 15","pages":"1688–1704"},"PeriodicalIF":2.9,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.organomet.5c00171","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144806865","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 and Characterization of Terphenyl Phosphine Ligands and Their Palladium Catalyst Precursors","authors":"Lixue Zhang,&nbsp;Fabin Zhou,&nbsp;Guoyu Cheng,&nbsp;Xin Yang,&nbsp;Duoduo Xiao,&nbsp;Dahong Jiang,&nbsp;Huicheng Cheng*,&nbsp;Bingxin Yuan* and Ji-cheng Shi*,&nbsp;","doi":"10.1021/acs.organomet.5c00129","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00129","url":null,"abstract":"<p >Terphenyl phosphines are rising as powerful supporting ligands for palladium-catalyzed C–N coupling reactions. Sixteen terphenyl phosphines <b>L1–16</b> with varying electronic and steric properties and their precatalysts of 2′-aminobiphenyl-2-yl-η²-C,N palladium(II) triflates (<b>tP1–16</b>) and allyl palladium triflates (<b>tA1–16</b>) were synthesized and characterized by ¹H, ¹³C, and ³¹P nuclear magnetic resonance (NMR) spectroscopy, and the complexes [(<b>L3</b>)(2′-aminobiphenyl-2-yl-η²-C,N)Pd]OTf (<b>tP3</b>), [(<b>L7</b>)(2′-aminobiphenyl-2-yl-η²-C,N)Pd]OTf (<b>tP7</b>), and [(<b>L4</b>)(allyl)Pd]OTf (<b>tA4</b>) were confirmed by single-crystal X-ray diffraction. The cross-coupling of 4-chloroanisole and 4-methoxyphenyl amine by <b>tP1–16</b> suggests that the combination of 2,4,6-triisopropyl groups on the terphenyl skeleton and the two cyclohexyl groups on the phosphorus atoms is important for the excellent catalytic performance of the palladium-catalyzed C–N cross-coupling reaction.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 15","pages":"1653–1659"},"PeriodicalIF":2.9,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144806797","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":"C–C Bond Formation at an Aluminacyclopropane","authors":"Andrea O’Reilly,&nbsp;J. Robin Fulton* and Martyn P. Coles*,&nbsp;","doi":"10.1021/acs.organomet.5c00169","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00169","url":null,"abstract":"<p >The reactivity of the aluminacyclopropane compound K[Al(NON)(η²-C₂H₄)] (NON = κ<i>N</i>,<i>N</i>’-[O(SiMe₂NDipp)₂]^2–; Dipp = 2,6-<i>i</i>Pr₂C₆H₃) toward isocyanides R–NC (R = Cy, Ad, <i>t</i>Bu; Cy = cyclohexyl, Ad = 1-adamantyl) and benzophenone is described. All reactions proceed via insertion of the substrate into an Al–C bond of the aluminacycle, with C–C bond formation leading to ring-expanded products. With isocyanide substrates, either monoinsertion (R = Cy, Ad, <i>t</i>Bu) to afford the four-membered aluminacyclobuta-1-imine ring, or double insertion (R = <i>t</i>Bu) to form an aluminacyclopenta-1,2-diimine ring is observed. The reaction with benzophenone affords the corresponding insertion product that incorporates the C═O functionality to form an expanded five-membered AlOC₃ ’alumina-tetrahydrofuran’ ring. The NON-ligand of this product undergoes a thermally induced, intramolecular 1,3-silyl retro-Brook rearrangement to afford the corresponding “Al(NNO)” product ([NNO]^2– = κ<i>N</i>,<i>O</i>-[N(Dipp)SiMe₂N(Dipp)SiMe₂O]^2–).</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 15","pages":"1679–1687"},"PeriodicalIF":2.9,"publicationDate":"2025-07-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144806853","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":"Kinetic Stabilization in Diaryl-Substituted Stannylenes: N2O Reactivity, Intramolecular C–H Activation, and Crystalline (Eind)Li(THF)2 as a Versatile Precursor in Tin Chemistry","authors":"Miray Aklan,&nbsp;Jonathan Kieselbach,&nbsp;Christopher Golz and Malte Fischer*,&nbsp;","doi":"10.1021/acs.organomet.5c00203","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00203","url":null,"abstract":"<p >The reactivity of the kinetically stabilized stannylene (^MesTer)₂Sn (<b>1</b>) (^MesTer = –C₆H₃-2,6-(2,4,6-Me₃-C₆H₂)₂) toward N₂O is revisited, yielding the terminal tin(IV) hydroxide <b>2</b> via formal intramolecular C(sp³)–H activation of a putative terminal stannanone intermediate. By switching to Eind ligation (Eind = 1,1,3,3,5,5,7,7-octaethyl-<i>s</i>-hydrindacen-4-yl) at the tin center, the synthesis and characterization of the crystalline lithium salt (Eind)Li(THF)₂ (<b>3</b>) is reported, serving as a straightforward precursor for the clean generation of the corresponding stannylene (Eind)₂Sn (<b>4</b>). Compound <b>4</b> can be further cleanly converted into the heteroleptic Eind/halide stannylene (Eind)SnCl (<b>6</b>). Both <b>4</b> and <b>6</b> serve as suitable precursors for the synthesis of the heteroleptic <i>s</i>-hydrindacene-/amido-substituted stannylene (Eind)Sn{N(SiMe₃)₂} (<b>5</b>).</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 15","pages":"1705–1712"},"PeriodicalIF":2.9,"publicationDate":"2025-07-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.organomet.5c00203","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144806968","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":"Flash Communication: Gram-Scale Synthesis of White Phosphorus, P4","authors":"Christine M. Thomas*,&nbsp;Tianze Song and Joshua E. Goldberger*,&nbsp;","doi":"10.1021/acs.organomet.5c00222","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00222","url":null,"abstract":"<p >A convenient chemical vapor transport approach is reported for the preparation of white phosphorus, P₄, on a gram scale. The activation of P₄ has long fascinated main group and transition metal chemists, who have sought a greener route to directly convert this allotrope of phosphorus to organophosphorus compounds. However, the absence of a commercial supplier of P₄ has hindered the thorough exploration of this small molecule’s activation and functionalization. Although methods for the generation of P₄ from red phosphorus have been reported, safety considerations associated with these methods necessitated the development of a safer alternative synthetic route. Herein, we report a method for the preparation of pure white phosphorus, P₄, by heating its readily available red phosphorus allotrope in a sealed quartz tube across a large temperature gradient.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 14","pages":"1515–1517"},"PeriodicalIF":2.9,"publicationDate":"2025-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144806594","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":"Controlled Polymerization of 3-Hexyne, 4-Octyne, and 5-Decyne by Nb(CHCMe2Ph)(NC6F5)[OC(CF3)3](PMe3)2 Catalyst: Structural Analysis of Catalytically Inactive Species","authors":"Akito Nishiyama,&nbsp;Kanchana Chatchaipaiboon and Kotohiro Nomura*,&nbsp;","doi":"10.1021/acs.organomet.5c00177","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00177","url":null,"abstract":"<p >Reaction of Nb(CHSiMe₃)(NAr)[OC(CF₃)₃](PMe₃)₂ (Ar = 2,6-Me₂C₆H₃, C₆F₅) with 3-hexyne (10 equiv) afforded alkyne coordinated species, Nb(NAr)[OC(CF₃)₃](EtC═CEt)(PMe₃)₂, accompanied by formation of 1-trimethylsilyl-2,3,4,5-tetraethyl-1,3-cyclopentadiene, which was inactive for 3-hexyne polymerization. In contrast, the neophylidene analogue Nb(CHCMe₂Ph)(NC₆F₅)[OC(CF₃)₃](PMe₃)₂ enabled polymerizations of 3-hexyne, 4-octyne, and 5-decyne to proceed efficiently in a controlled manner without formation of inactive species.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 15","pages":"1633–1638"},"PeriodicalIF":2.9,"publicationDate":"2025-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.organomet.5c00177","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144806620","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}