Dr. Jesús Bello-García, Prof. Jesús A. Varela, Prof. Carlos Saá
Annulenes. In their Communication (e202414017), Jesús Bello-García, Jesús A. Varela, and Carlos Saá report the K+-mediated versus Pd-catalyzed cyclotrimerization of 9,10-didehydrotribenzo[8]annulene to access stereodivergent fragments of cubic graphite.
烯。Jesús Bello-García、Jesús A. Varela 和 Carlos Saá 在他们的通讯（e202414017）中报告了 K+ 介导和 Pd 催化的 9,10-二脱氢三苯并[8]烯环三聚反应，从而获得立方石墨的立体异构片段。
{"title":"Frontispiz: K+-Mediated vs Pd-Catalyzed Cyclotrimerization of 9,10-Didehydrotribenzo[8]annulene (TribenzoCOTyne): Stereodivergent Access to (α,α,α)- and (α,α,β)-Fragments of Cubic Graphite","authors":"Dr. Jesús Bello-García, Prof. Jesús A. Varela, Prof. Carlos Saá","doi":"10.1002/ange.202484962","DOIUrl":"https://doi.org/10.1002/ange.202484962","url":null,"abstract":"<p><b>Annulenes</b>. In their Communication (e202414017), Jesús Bello-García, Jesús A. Varela, and Carlos Saá report the K+-mediated versus Pd-catalyzed cyclotrimerization of 9,10-didehydrotribenzo[8]annulene to access stereodivergent fragments of cubic graphite.\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"136 49","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-11-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ange.202484962","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142708102","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jiankang Gong, Xiaoyu Wang, Jiao Wu, Changyu Yoon, Yujin Kim, Jingwen Zou, Prof. Zhiqiang Mao, Prof. Jong Seung Kim
Fluorescent Probes. In their Research Article (e202409295), Zhiqiang Mao, Jong Seung Kim et al. introduce a diaminonaphthalene-protected boronic acid as a universal and highly selective recognition group for ONOO− over H2O2 and other reactive oxygen species, overcoming the long-standing issues of aryl-boronic acid-based probes.
荧光探针。毛志强、Jong Seung Kim 等人在他们的研究文章（e202409295）中介绍了一种二氨基萘保护的硼酸，它是 ONOO- 而不是 H2O2 和其他活性氧的通用和高选择性识别基团，克服了长期以来芳基硼酸探针存在的问题。
{"title":"Frontispiz: Diaminonaphthalene Boronic Acid (DANBA): New Approach for Peroxynitrite Sensing Site","authors":"Jiankang Gong, Xiaoyu Wang, Jiao Wu, Changyu Yoon, Yujin Kim, Jingwen Zou, Prof. Zhiqiang Mao, Prof. Jong Seung Kim","doi":"10.1002/ange.202484961","DOIUrl":"https://doi.org/10.1002/ange.202484961","url":null,"abstract":"<p><b>Fluorescent Probes</b>. In their Research Article (e202409295), Zhiqiang Mao, Jong Seung Kim et al. introduce a diaminonaphthalene-protected boronic acid as a universal and highly selective recognition group for ONOO<sup>−</sup> over H<sub>2</sub>O<sub>2</sub> and other reactive oxygen species, overcoming the long-standing issues of aryl-boronic acid-based probes.\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"136 49","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-11-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ange.202484961","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142708101","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Hengjun Liu, Yong Jiang, Qingqing Li, Dr. Guangtong Hai, Dr. Chao Gu, Prof. Dr. Yaping Du
Rare earth (RE) elements are attractive for spin-magnetic modulation due to their unique 4f electron configuration and strong orbital couplings. In their Research Article (e202412591), Chao Gu, Yaping Du et al. define a solid-phase synthetic protocol for creating RE-3d transition metal–noble metal integrated intraparticle heterostructured nanoalloys with distinct Gd and Co interface within the entire Rh framework. They exhibit interface-triggered antiferromagnetic interaction, which can induce electron redistribution and regulate spin polarization.
{"title":"Innenrücktitelbild: Interface-Triggered Spin-Magnetic Effect in Rare Earth Intraparticle Heterostructured Nanoalloys for Boosting Hydrogen Evolution (Angew. Chem. 52/2024)","authors":"Hengjun Liu, Yong Jiang, Qingqing Li, Dr. Guangtong Hai, Dr. Chao Gu, Prof. Dr. Yaping Du","doi":"10.1002/ange.202422061","DOIUrl":"https://doi.org/10.1002/ange.202422061","url":null,"abstract":"<p><b>Rare earth</b> (RE) elements are attractive for spin-magnetic modulation due to their unique 4f electron configuration and strong orbital couplings. In their Research Article (e202412591), Chao Gu, Yaping Du et al. define a solid-phase synthetic protocol for creating RE-3d transition metal–noble metal integrated intraparticle heterostructured nanoalloys with distinct Gd and Co interface within the entire Rh framework. They exhibit interface-triggered antiferromagnetic interaction, which can induce electron redistribution and regulate spin polarization.\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"136 52","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-11-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ange.202422061","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142851546","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Matthieu Haake, Dr. Bertrand Reuillard, Dr. Murielle Chavarot-Kerlidou, Prof. Cyrille Costentin, Dr. Vincent Artero
The active sites of metalloenzymes involved in small molecules activation often contain pendant bases that act as proton relay promoting proton-coupled electron-transfer processes. Here we focus on hydrogenases and on the reactions they catalyze, i. e. the hydrogen evolution and oxidation reactions. After a short description of these enzymes, we review some of the various biomimetic and bioinspired molecular systems that contain proton relays. We then provide the formal electrochemical framework required to decipher the key role of such proton relay to enhance catalysis in a single direction and discuss the few systems active for H2 evolution for which quantitative kinetic data are available. We finally highlight key parameters required to reach bidirectional catalysis (both hydrogen evolution and hydrogen oxidation catalyzed) and then transition to reversible catalysis (both reactions catalyzed in a narrow potential range) as well as illustrate these features on few systems from the literature.
{"title":"Proton Relays in Molecular Catalysis for Hydrogen Evolution and Oxidation: Lessons From the Mimicry of Hydrogenases and Electrochemical Kinetic Analyses","authors":"Matthieu Haake, Dr. Bertrand Reuillard, Dr. Murielle Chavarot-Kerlidou, Prof. Cyrille Costentin, Dr. Vincent Artero","doi":"10.1002/ange.202413910","DOIUrl":"https://doi.org/10.1002/ange.202413910","url":null,"abstract":"<p>The active sites of metalloenzymes involved in small molecules activation often contain pendant bases that act as proton relay promoting proton-coupled electron-transfer processes. Here we focus on hydrogenases and on the reactions they catalyze, i. e. the hydrogen evolution and oxidation reactions. After a short description of these enzymes, we review some of the various biomimetic and bioinspired molecular systems that contain proton relays. We then provide the formal electrochemical framework required to decipher the key role of such proton relay to enhance catalysis in a single direction and discuss the few systems active for H<sub>2</sub> evolution for which quantitative kinetic data are available. We finally highlight key parameters required to reach bidirectional catalysis (both hydrogen evolution and hydrogen oxidation catalyzed) and then transition to reversible catalysis (both reactions catalyzed in a narrow potential range) as well as illustrate these features on few systems from the literature.</p>","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"136 52","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ange.202413910","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142851330","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Dr. Ehsan Hamzehpoor, Farshid Effaty, Dr. Tristan H. Borchers, Dr. Robin S. Stein, Dr. Alexander Wahrhaftig-Lewis, Prof. Xavier Ottenwaelder, Prof. Tomislav Friščić, Prof. Dmytro F. Perepichka
Mechanochemistry …. … can be used in the synthesis of covalent organic frameworks (COFs), as reported by Xavier Ottenwaelder, Tomislav Friščić, Dmytro F. Perepichka et al. in their Research Article (e202404539). Based on this concept the first mechanochemical synthesis of boroxine-based 2D and 3D COFs with high surface area of up to 2,500 m2 g−1 was developed. The cover picture shows the structure of the monomers and the COF with the electron micrograph of the mechanochemically prepared COF in the background.
机械化学……Xavier Ottenwaelder, Tomislav Friščić， Dmytro F. Perepichka等人报道…可用于合成共价有机框架（COFs）。在他们的研究文章（e202404539）中。基于这一概念，开发了第一个机械化学合成的基于硼氧辛的2D和3D COFs，其高表面积高达2,500 m2 g−1。封面图片显示了单体和COF的结构，背景是机械化学制备的COF的电子显微照片。
{"title":"Titelbild: Mechanochemical Synthesis of Boroxine-linked Covalent Organic Frameworks (Angew. Chem. 51/2024)","authors":"Dr. Ehsan Hamzehpoor, Farshid Effaty, Dr. Tristan H. Borchers, Dr. Robin S. Stein, Dr. Alexander Wahrhaftig-Lewis, Prof. Xavier Ottenwaelder, Prof. Tomislav Friščić, Prof. Dmytro F. Perepichka","doi":"10.1002/ange.202421733","DOIUrl":"https://doi.org/10.1002/ange.202421733","url":null,"abstract":"<p><b>Mechanochemistry …</b>. … can be used in the synthesis of covalent organic frameworks (COFs), as reported by Xavier Ottenwaelder, Tomislav Friščić, Dmytro F. Perepichka et al. in their Research Article (e202404539). Based on this concept the first mechanochemical synthesis of boroxine-based 2D and 3D COFs with high surface area of up to 2,500 m<sup>2</sup> g<sup>−1</sup> was developed. The cover picture shows the structure of the monomers and the COF with the electron micrograph of the mechanochemically prepared COF in the background.\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"136 51","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ange.202421733","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142861767","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Dr. Huai-Bin Yang, Xiang Zhao, Quan Wang, Yu-Hong Ruan, Zhao-Xiang Liu, Xin Yue, Dr. Yin Bo Zhu, Prof. Heng An Wu, Dr. Qing-Fang Guan, Prof. Shu-Hong Yu
Organic Materials. An all-natural structural material is simultaneously strengthened and toughened through its interfacial interlocking structure and intermolecular interactions, as reported by Shu-Hong Yu et al. in their Research Article (e202408458).
{"title":"Frontispiz: Simultaneously Strengthening and Toughening All-Natural Structural Materials via 3D Nanofiber Network Interfacial Design","authors":"Dr. Huai-Bin Yang, Xiang Zhao, Quan Wang, Yu-Hong Ruan, Zhao-Xiang Liu, Xin Yue, Dr. Yin Bo Zhu, Prof. Heng An Wu, Dr. Qing-Fang Guan, Prof. Shu-Hong Yu","doi":"10.1002/ange.202484861","DOIUrl":"https://doi.org/10.1002/ange.202484861","url":null,"abstract":"<p><b>Organic Materials</b>. An all-natural structural material is simultaneously strengthened and toughened through its interfacial interlocking structure and intermolecular interactions, as reported by Shu-Hong Yu et al. in their Research Article (e202408458).\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"136 48","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ange.202484861","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142665749","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Liexin Wu, Dr. Lu Zhang, Dr. Jiandong Guo, Jihui Gao, Yang Ding, Dr. Jie Ke, Prof. Dr. Chuan He
Asymmetric Hydrosilylation. In their Communication (e202413753), Chuan He et al. report an efficient Cu-catalyzed asymmetric cascade hydrosilylation protocol, which allows the rapid assembly of carbon- and silicon-stereogenic silacyclopentanes with good to excellent enantioselectivities and diastereoselectivities.
不对称氢硅烷化。在他们的通讯（e202413753）中，Chuan He 等人报告了一种高效的铜催化不对称级联氢硅烷化协议，该协议可快速组装碳和硅立体硅环戊烷，并具有良好至卓越的对映选择性和非对映选择性。
{"title":"Frontispiz: Catalytic Asymmetric Construction of C- and Si-Stereogenic Silacyclopentanes via Hydrosilylation of Arylmethylenecyclopropanes","authors":"Liexin Wu, Dr. Lu Zhang, Dr. Jiandong Guo, Jihui Gao, Yang Ding, Dr. Jie Ke, Prof. Dr. Chuan He","doi":"10.1002/ange.202484862","DOIUrl":"https://doi.org/10.1002/ange.202484862","url":null,"abstract":"<p><b>Asymmetric Hydrosilylation</b>. In their Communication (e202413753), Chuan He et al. report an efficient Cu-catalyzed asymmetric cascade hydrosilylation protocol, which allows the rapid assembly of carbon- and silicon-stereogenic silacyclopentanes with good to excellent enantioselectivities and diastereoselectivities.\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"136 48","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ange.202484862","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142665751","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Leon K. Paschai Darian, Prof. Joachim Ballmann, Prof. Lutz H. Gade
<p>Dreifach koordinierte 14-Valenzelektronen-Rhodiumkomplexe werden als aktive Spezies in verschiedenen katalytischen Umwandlungen im industriellen Maßstab postuliert.<span><sup>1</sup></span> Dazu gehören Hydrierungen mit dem Wilkinson Katalysator,<span><sup>2</sup></span> aber auch Aryl/Alkinyl-H- oder Aryl/Silyl-X Additionsreaktionen,<span><sup>3</sup></span> Carbonylierungen<span><sup>4</sup></span> sowie Alkandehydrierungen.<span><sup>5</sup></span> Insbesondere bei Letzteren sind C−H-Aktivierungen die Schlüsselschritte, weshalb diese Reaktivität mit transienten ungesättigten Rh(I)<span><sup>6</sup></span> und Ir(I)<span><sup>7</sup></span> Spezies intensiv erforscht worden ist.</p><p>Solche koordinativ ungesättigte 14-Elektronen-Rh(I)-Komplexe wurden in situ entweder aus geeigneten Vorläufern erzeugt, welche durch Dissoziation schwach bindender Donor-Liganden<span><sup>3c</sup></span> oder durch reversible C−H-Aktivierung aus einem cyclometallierten Rh(III)-Komplex erhalten wurden.<span><sup>8</sup></span> Die Isolierung und vollständig Charakterisierung dieser Verbindungen ist jedoch nur in wenigen Fällen und dann auf Kosten ihrer Neigung zur C−H-Aktivierung gelungen, wie sie bei den katalytisch aktiven Spezies ausgeprägt ist.<span><sup>9</sup></span> Erwähnenswert ist, dass in einer Reihe grundlegender Untersuchungen ein σ-Methan-Rhodiumkomplex sowie mehrere σ-Alkan-Rhodiumkomplexe sowohl in Lösung als auch im Festkörper charakterisiert wurden, ohne dass diese zu den C−H-aktivierten Produkten reagierten.<span><sup>10</sup></span></p><p>Vor dem Hintergrund der Fähigkeit des Cbzdiphos-PNP<sup>R</sup>-Pincer-Liganden, koordinativ hochgradig ungesättigte, T-förmige Übergangsmetallkomplexe zu stabilisieren,<span><sup>11</sup></span> wurde der Versuch unternommen, eine neutrale 14-Elektronen-Rhodium(I)-Spezies „einzurahmen“, deren Potenzial für oxidative C−H-Addition an das Metallzentrum erhalten bleiben sollte (Abbildung 1). </p><p>Durch Deprotonierung der Bis(<i>t</i>-butyl)phosphino- und bis(1-Adamantyl)phosphino-substituierten Cbzdiphos-PNP<sup>R</sup>-Protio-Liganden <b>1 a</b> und <b>1 b</b> mit LiHMDS und in situ-Reaktion mit [Rh(COE)<sub>2</sub>Cl]<sub>2</sub> in Toluol für <b>1 a</b>, beziehungsweise die Isolierung des deprotonierten Liganden und die anschließende Reaktion in Cyclopentan für <b>1 b</b>, wurden die entsprechenden Rhodiumkomplexe <b>2 a</b> und <b>2 b</b> erhalten (Schema 1).</p><p>Die Reaktionsprodukte <b>2 a</b> und <b>2 b</b> wiesen in Lösung deutliche unterschiedliche NMR-Eigenschaften auf. Während die bei 295 K aufgezeichneten <sup>1</sup>H- und <sup>31</sup>P NMR-Spektren von <b>2 a</b> mit effektiver C<sub>2v</sub>-Symmetrie in Lösung in Einklang waren, was auf eine schnelle dynamische Inversion des Carbazolgerüsts auf der NMR-Zeitskala zurückzuführen ist, waren die Resonanzen für die <i>t</i>-Butylphosphin-Substituenten breit und die <i>J</i>-Kopplungen nicht aufgelöst.</p><p>Abkühlen auf 190 K führte zur Dekoale
{"title":"T-förmige 14 Elektronen-Rhodiumkomplexe: Potentiell aktive Spezies in CH-Aktivierungen","authors":"Leon K. Paschai Darian, Prof. Joachim Ballmann, Prof. Lutz H. Gade","doi":"10.1002/ange.202416814","DOIUrl":"https://doi.org/10.1002/ange.202416814","url":null,"abstract":"<p>Dreifach koordinierte 14-Valenzelektronen-Rhodiumkomplexe werden als aktive Spezies in verschiedenen katalytischen Umwandlungen im industriellen Maßstab postuliert.<span><sup>1</sup></span> Dazu gehören Hydrierungen mit dem Wilkinson Katalysator,<span><sup>2</sup></span> aber auch Aryl/Alkinyl-H- oder Aryl/Silyl-X Additionsreaktionen,<span><sup>3</sup></span> Carbonylierungen<span><sup>4</sup></span> sowie Alkandehydrierungen.<span><sup>5</sup></span> Insbesondere bei Letzteren sind C−H-Aktivierungen die Schlüsselschritte, weshalb diese Reaktivität mit transienten ungesättigten Rh(I)<span><sup>6</sup></span> und Ir(I)<span><sup>7</sup></span> Spezies intensiv erforscht worden ist.</p><p>Solche koordinativ ungesättigte 14-Elektronen-Rh(I)-Komplexe wurden in situ entweder aus geeigneten Vorläufern erzeugt, welche durch Dissoziation schwach bindender Donor-Liganden<span><sup>3c</sup></span> oder durch reversible C−H-Aktivierung aus einem cyclometallierten Rh(III)-Komplex erhalten wurden.<span><sup>8</sup></span> Die Isolierung und vollständig Charakterisierung dieser Verbindungen ist jedoch nur in wenigen Fällen und dann auf Kosten ihrer Neigung zur C−H-Aktivierung gelungen, wie sie bei den katalytisch aktiven Spezies ausgeprägt ist.<span><sup>9</sup></span> Erwähnenswert ist, dass in einer Reihe grundlegender Untersuchungen ein σ-Methan-Rhodiumkomplex sowie mehrere σ-Alkan-Rhodiumkomplexe sowohl in Lösung als auch im Festkörper charakterisiert wurden, ohne dass diese zu den C−H-aktivierten Produkten reagierten.<span><sup>10</sup></span></p><p>Vor dem Hintergrund der Fähigkeit des Cbzdiphos-PNP<sup>R</sup>-Pincer-Liganden, koordinativ hochgradig ungesättigte, T-förmige Übergangsmetallkomplexe zu stabilisieren,<span><sup>11</sup></span> wurde der Versuch unternommen, eine neutrale 14-Elektronen-Rhodium(I)-Spezies „einzurahmen“, deren Potenzial für oxidative C−H-Addition an das Metallzentrum erhalten bleiben sollte (Abbildung 1).\u0000</p><p>Durch Deprotonierung der Bis(<i>t</i>-butyl)phosphino- und bis(1-Adamantyl)phosphino-substituierten Cbzdiphos-PNP<sup>R</sup>-Protio-Liganden <b>1 a</b> und <b>1 b</b> mit LiHMDS und in situ-Reaktion mit [Rh(COE)<sub>2</sub>Cl]<sub>2</sub> in Toluol für <b>1 a</b>, beziehungsweise die Isolierung des deprotonierten Liganden und die anschließende Reaktion in Cyclopentan für <b>1 b</b>, wurden die entsprechenden Rhodiumkomplexe <b>2 a</b> und <b>2 b</b> erhalten (Schema 1).</p><p>Die Reaktionsprodukte <b>2 a</b> und <b>2 b</b> wiesen in Lösung deutliche unterschiedliche NMR-Eigenschaften auf. Während die bei 295 K aufgezeichneten <sup>1</sup>H- und <sup>31</sup>P NMR-Spektren von <b>2 a</b> mit effektiver C<sub>2v</sub>-Symmetrie in Lösung in Einklang waren, was auf eine schnelle dynamische Inversion des Carbazolgerüsts auf der NMR-Zeitskala zurückzuführen ist, waren die Resonanzen für die <i>t</i>-Butylphosphin-Substituenten breit und die <i>J</i>-Kopplungen nicht aufgelöst.</p><p>Abkühlen auf 190 K führte zur Dekoale","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"136 52","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ange.202416814","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142861476","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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