The use of readily available prochiral or racemic quaternary carbons to access enantioenriched ones offers a promising alternative to conventional synthesis from tertiary or planar substrates. Unlike desymmetrization that modifies an existing substituent with limited reactivity, a functional group swap can install a new motif that is structurally distinct and non-derivable from the replaced group. However, achieving enantioconvergence in these quaternary-to-quaternary transformations is challenging, especially for acyclic stereocenters. Here, we report that acyl groups of β-ketonitriles can be stereoselectively replaced by allyl, propargyl, or benzyl moieties using easily accessible alcohols under palladium catalysis. The deacylative functionalization proceeds through a retro-Claisen-type elimination of ketonitrile with alkoxide and the absence of diastereoisomerism in the resulting ketenimine anion assists the subsequent asymmetric addition. Together with the pair of α-substituents, the retained nitrile and the incoming alkyl motif instill significant derivatization potential into the enantioenriched quaternary stereocenters.
{"title":"Enantioconvergent Deacylative Functionalization towards α-Quaternary Nitriles","authors":"Minghao Zhang, Zhongxing Huang","doi":"10.1002/anie.202503149","DOIUrl":"https://doi.org/10.1002/anie.202503149","url":null,"abstract":"The use of readily available prochiral or racemic quaternary carbons to access enantioenriched ones offers a promising alternative to conventional synthesis from tertiary or planar substrates. Unlike desymmetrization that modifies an existing substituent with limited reactivity, a functional group swap can install a new motif that is structurally distinct and non-derivable from the replaced group. However, achieving enantioconvergence in these quaternary-to-quaternary transformations is challenging, especially for acyclic stereocenters. Here, we report that acyl groups of β-ketonitriles can be stereoselectively replaced by allyl, propargyl, or benzyl moieties using easily accessible alcohols under palladium catalysis. The deacylative functionalization proceeds through a retro-Claisen-type elimination of ketonitrile with alkoxide and the absence of diastereoisomerism in the resulting ketenimine anion assists the subsequent asymmetric addition. Together with the pair of α-substituents, the retained nitrile and the incoming alkyl motif instill significant derivatization potential into the enantioenriched quaternary stereocenters.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"56 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143660854","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Andriy Luzhetskyy, Stepan Tistechok, Dmytro Bratiichuk, Hilda Sucipto, Nils Gummerlich, Marc Stierhof, Franziska Fries, Rolf Müller, Josef Zapp, Maksym Myronovskyi, Oleksandr Gromyko, Victor Fedorenko
The current situation with drug-resistant microbial pathogens is critical dictating an acute need for novel efficient antibiotics. Herein, we report a new class of antibiotics entitled gromomycins with significant activity especially against drug-resistant Gram-positive pathogens including methicillin- and daptomycin-resistant Staphylococcus aureus. Gromomycins are pentacyclic triterpenes with a cyclic guanidino group forming the fifth six-membered ring. We have used transposon mutagenesis to identify the gromomycin biosynthetic gene cluster since it could not be assigned by any available bioinformatics tools, highlighting its unique biosynthetic route. Using gene cluster engineering, feeding experiments, LC-MS and NMR analyses we have proposed the biosynthetic pathway for gromomycins, which are the first bacterial triterpenes synthesized independently of the squalene pathway. They also exhibit a so far unprecedented cyclization route that utilizes a hexaprenylguanidine linear precursor. Leveraging our understanding of their biosynthesis, we have identified additional gromomycin producers, resulting in the isolation of novel bioactive derivatives.
{"title":"Gromomycins: An Unprecedented Class of Triterpene Antibiotics Produced by a Novel Biosynthetic Pathway","authors":"Andriy Luzhetskyy, Stepan Tistechok, Dmytro Bratiichuk, Hilda Sucipto, Nils Gummerlich, Marc Stierhof, Franziska Fries, Rolf Müller, Josef Zapp, Maksym Myronovskyi, Oleksandr Gromyko, Victor Fedorenko","doi":"10.1002/anie.202422270","DOIUrl":"https://doi.org/10.1002/anie.202422270","url":null,"abstract":"The current situation with drug-resistant microbial pathogens is critical dictating an acute need for novel efficient antibiotics. Herein, we report a new class of antibiotics entitled gromomycins with significant activity especially against drug-resistant Gram-positive pathogens including methicillin- and daptomycin-resistant Staphylococcus aureus. Gromomycins are pentacyclic triterpenes with a cyclic guanidino group forming the fifth six-membered ring. We have used transposon mutagenesis to identify the gromomycin biosynthetic gene cluster since it could not be assigned by any available bioinformatics tools, highlighting its unique biosynthetic route. Using gene cluster engineering, feeding experiments, LC-MS and NMR analyses we have proposed the biosynthetic pathway for gromomycins, which are the first bacterial triterpenes synthesized independently of the squalene pathway. They also exhibit a so far unprecedented cyclization route that utilizes a hexaprenylguanidine linear precursor. Leveraging our understanding of their biosynthesis, we have identified additional gromomycin producers, resulting in the isolation of novel bioactive derivatives.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"21 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143660763","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Single-atom catalysts (SACs) are regarded as effective electrocatalysts for oxygen reduction reaction (ORR). However, integrating high active and long-term durability on SACs is still challenging due to the severe limitations of activity-stability trade-off. Herein, we report an integrative electrocatalyst combining isolated Fe sites and MoC nanoparticles (MoC/Fe-NC). MoC nanoparticles accelerate ORR kinetics via the proton-feeding effect and optimize Fe site microstructure. Thus, MoC/Fe-NC exhibits a high alkaline ORR activity with half-wave potential (E1/2) of 0.916 V vs. the reversible hydrogen electrode, and exceptional durability of 50k cycles with 5 mV E1/2 loss. The observed ORR performance is further verified in a zinc-air battery (ZAB) with a high peak power density of 316 mW cm−2 and operational stability over 1000 h. Moreover, the fabricated temperature-adaptive quasi-solid-state ZAB can cycle stably for 150 h under alternating temperatures. Theory calculations and experiment characterizations, involving scanning electrochemical microscopy techniques and distribution of relaxation times analysis, reveal that the excellent capabilities of MoC/Fe-NC arise from accelerated proton-coupled electron transfer, weakened *OH adsorption, and strengthened Fe−N bonds fueled by MoC nanoparticles. This work sheds light on breaking the activity-stability trade-off barrier of SACs for energy-conversion applications.
{"title":"Engineering Proton-Coupled Electron Transfer to Break Activity-Stability Trade-off of Oxygen Electroreduction Catalysts for Temperature-Adaptive Zn-Air Battery","authors":"Yonggan Wu, Yuqin Zhang, Liansheng Lan, Ting Hu, Shaobin Tang, Dirk Lützenkirchen-Hecht, Kai Yuan, Yiwang Chen","doi":"10.1002/anie.202502019","DOIUrl":"https://doi.org/10.1002/anie.202502019","url":null,"abstract":"Single-atom catalysts (SACs) are regarded as effective electrocatalysts for oxygen reduction reaction (ORR). However, integrating high active and long-term durability on SACs is still challenging due to the severe limitations of activity-stability trade-off. Herein, we report an integrative electrocatalyst combining isolated Fe sites and MoC nanoparticles (MoC/Fe-NC). MoC nanoparticles accelerate ORR kinetics via the proton-feeding effect and optimize Fe site microstructure. Thus, MoC/Fe-NC exhibits a high alkaline ORR activity with half-wave potential (E1/2) of 0.916 V vs. the reversible hydrogen electrode, and exceptional durability of 50k cycles with 5 mV E1/2 loss. The observed ORR performance is further verified in a zinc-air battery (ZAB) with a high peak power density of 316 mW cm−2 and operational stability over 1000 h. Moreover, the fabricated temperature-adaptive quasi-solid-state ZAB can cycle stably for 150 h under alternating temperatures. Theory calculations and experiment characterizations, involving scanning electrochemical microscopy techniques and distribution of relaxation times analysis, reveal that the excellent capabilities of MoC/Fe-NC arise from accelerated proton-coupled electron transfer, weakened *OH adsorption, and strengthened Fe−N bonds fueled by MoC nanoparticles. This work sheds light on breaking the activity-stability trade-off barrier of SACs for energy-conversion applications.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"61 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143660764","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The use of clean electric energy to activate inert compounds has garnered significant attention. Homogeneous redox mediators (RMs) in organic electrosynthesis are effective platforms for this purpose. However, understanding the RM's electronic structure under operational conditions, electron transport processes at the electrode surface, and substrate adsorption-desorption dynamics remains challenging. Here, we synthesized a Cu single-atom catalyst (SAC, named Cu-N-P@NC) with a CuN3P1 micro-coordination structure, employing it as a unique cathode redox mediator. Introducing phosphine atoms into the coordination system allowed modulation of the SAC's electronic metal-support interaction, optimizing catalyst-substrate adsorption-desorption dynamics and accelerating electrochemical reactions. Utilizing the heterogeneous SAC strategy, we achieved a novel electro-reduction coupling ring-opening reaction of inert quinazolinone frameworks. The Cu-SAC exhibited exceptionally high catalytic activity and substrate compatibility, operating smoothly at gram-scale production. Additionally, we applied the SAC to modify 11 natural product molecules. Integrating micro-coordination environment regulation and theoretical adsorption models elucidated the significant influence of electrode-RMs-substrate interactions on reaction kinetics and catalytic efficiency-a feat challenging for homogeneous RMs. This approach offers a novel pathway for advancing efficient organic electrosynthesis reactions and provides critical insights for mechanistic studies.
{"title":"Phosphorus-Doped Single Atom Copper Catalyst as a Redox Mediator in the Cathodic Reduction of Quinazolinones","authors":"Xin-Yu Wang, Wan-Jie Wei, Si-Yu Zhou, Yong-Zhou Pan, Jiarui Yang, Tao Gan, Zechao Zhuang, Wen-Hao Li, Xia Zhang, Ying-Ming Pan, Hai-Tao Tang, Dingsheng Wang","doi":"10.1002/anie.202505085","DOIUrl":"https://doi.org/10.1002/anie.202505085","url":null,"abstract":"The use of clean electric energy to activate inert compounds has garnered significant attention. Homogeneous redox mediators (RMs) in organic electrosynthesis are effective platforms for this purpose. However, understanding the RM's electronic structure under operational conditions, electron transport processes at the electrode surface, and substrate adsorption-desorption dynamics remains challenging. Here, we synthesized a Cu single-atom catalyst (SAC, named Cu-N-P@NC) with a CuN3P1 micro-coordination structure, employing it as a unique cathode redox mediator. Introducing phosphine atoms into the coordination system allowed modulation of the SAC's electronic metal-support interaction, optimizing catalyst-substrate adsorption-desorption dynamics and accelerating electrochemical reactions. Utilizing the heterogeneous SAC strategy, we achieved a novel electro-reduction coupling ring-opening reaction of inert quinazolinone frameworks. The Cu-SAC exhibited exceptionally high catalytic activity and substrate compatibility, operating smoothly at gram-scale production. Additionally, we applied the SAC to modify 11 natural product molecules. Integrating micro-coordination environment regulation and theoretical adsorption models elucidated the significant influence of electrode-RMs-substrate interactions on reaction kinetics and catalytic efficiency-a feat challenging for homogeneous RMs. This approach offers a novel pathway for advancing efficient organic electrosynthesis reactions and provides critical insights for mechanistic studies.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"8 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143660856","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Qiang Li, Yan Wang, Zhen hua Song, Xin tao Zhu, Xian wen Song, Yang Chen, Yi Zhang
Alkaline zinc-air batteries (ZABs) are recognized as a promising candidate for next generation of safe battery systems, owing to their inherent advantages. However, the performance of traditional ZABs is constrained by a lower theoretical voltage of 1.65 V, presenting a significant challenge in enhancing their practical application. This paper demonstrates a prototype of acid-alkaline hybrid quasi-solid-state zinc-air battery (HSZAB), featuring a unique design in both a new acidic gel electrolyte and battery structure. Our approach involves regulating the electrolyte pH and ionic conductivity to achieve an enhanced theoretical voltage, resulting in an open circuit voltage of up to 2.0 V. Additionally, the HSZAB demonstrates substantially improved peak power density (417 mW cm-², five times higher than the conventional alkaline ZABs) and increased energy efficiency (from 60% to 82%). This finding underscores the promising prospects of high voltage zinc-air batteries, offering a substantial step forward in the field of energy storage systems.
{"title":"High Voltage Design for Quasi-Solid Zinc-Air Batteries","authors":"Qiang Li, Yan Wang, Zhen hua Song, Xin tao Zhu, Xian wen Song, Yang Chen, Yi Zhang","doi":"10.1002/anie.202424318","DOIUrl":"https://doi.org/10.1002/anie.202424318","url":null,"abstract":"Alkaline zinc-air batteries (ZABs) are recognized as a promising candidate for next generation of safe battery systems, owing to their inherent advantages. However, the performance of traditional ZABs is constrained by a lower theoretical voltage of 1.65 V, presenting a significant challenge in enhancing their practical application. This paper demonstrates a prototype of acid-alkaline hybrid quasi-solid-state zinc-air battery (HSZAB), featuring a unique design in both a new acidic gel electrolyte and battery structure. Our approach involves regulating the electrolyte pH and ionic conductivity to achieve an enhanced theoretical voltage, resulting in an open circuit voltage of up to 2.0 V. Additionally, the HSZAB demonstrates substantially improved peak power density (417 mW cm-², five times higher than the conventional alkaline ZABs) and increased energy efficiency (from 60% to 82%). This finding underscores the promising prospects of high voltage zinc-air batteries, offering a substantial step forward in the field of energy storage systems.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"56 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143654015","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Helix assemblies of chiral molecules can transfer microscopic unimolecular chirality to macroscopic supramolecular chirality, enhancing various chiral properties. In addition to the commonly observed spiral-column-like helix assembly, a small number of spiral-stair-like helix assemblies have also been reported in aromatic nanocarbons with multiple chirality-related irregularities. However, they require separation of diastereomers and/or enantiomers or do not have stable chirality. Here, we report the enantio- and diastereoselective synthesis of figure-eight [10]cyclophenylenes with stable helical chirality by the rhodium-catalyzed four consecutive intramolecular [2+2+2] cycloadditions of dodecaynes with two flexible biphenyl units. The chiral figure-eight [10]cyclophenylene with ethyl and methyl side chains exhibits the spiral-stair-like single helix assembly in the crystal due to CH–π and CH–O interactions and good CPL properties in solution. Experimental verification of the enantio- and diastereodetermining steps of four consecutive [2+2+2] cycloadditions is also reported.
{"title":"Enantio- and Diastereoselective Synthesis and Spiral-Stair-Like Single Helix Assembly of Figure-Eight Cyclophenylenes","authors":"Kohei Adachi, Juntaro Nogami, Daisuke Hashizume, Daiki Tauchi, Masashi Hasegawa, Ken Tanaka","doi":"10.1002/anie.202502764","DOIUrl":"https://doi.org/10.1002/anie.202502764","url":null,"abstract":"Helix assemblies of chiral molecules can transfer microscopic unimolecular chirality to macroscopic supramolecular chirality, enhancing various chiral properties. In addition to the commonly observed spiral-column-like helix assembly, a small number of spiral-stair-like helix assemblies have also been reported in aromatic nanocarbons with multiple chirality-related irregularities. However, they require separation of diastereomers and/or enantiomers or do not have stable chirality. Here, we report the enantio- and diastereoselective synthesis of figure-eight [10]cyclophenylenes with stable helical chirality by the rhodium-catalyzed four consecutive intramolecular [2+2+2] cycloadditions of dodecaynes with two flexible biphenyl units. The chiral figure-eight [10]cyclophenylene with ethyl and methyl side chains exhibits the spiral-stair-like single helix assembly in the crystal due to CH–π and CH–O interactions and good CPL properties in solution. Experimental verification of the enantio- and diastereodetermining steps of four consecutive [2+2+2] cycloadditions is also reported.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"183 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143654020","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Lu Zhai, Jiayi Yuan, Jianyi Huang, Xue-Wei Pan, Li Wan, Weihua Ning, Xiao-Ming Ren
Circularly polarized luminescence (CPL)-active materials have attracted considerable attention due to their potential applications in various advanced technological fields. CPL activity typically requires compounds that crystallize in noncentrosymmetric chiral space groups. Achieving noncentrosymmetric crystal structures using achiral molecular architectures is highly appealing but remains a significant challenge. Herein, we present a strategy for designing and synthesizing high-performance CPL materials via crystallization-driven self-assembly using achiral architectures. We successfully obtained Mn2+-based halide enantiomeric hybrids (P-1 and M-1), self-assembled from [MnBr4]2- anions and rotational symmetric [Pr-dabco]2+ cations (Pr-dabco2+ = 1-Propyl-1,4-diazabicyclo-[2.2.2]octan-1-ium), crystallizing in the chiral space group P212121. The single crystals of 1 exhibit exceptionally high CPL performance, with a luminescence dissymmetry factor |glum| and photoluminescence quantum yield (PLQY) up to 4.8×10-2 and 86.8%, respectively, thus a record-high figure of merit (FM) of 4.2×10-2 among reported Mn2+-based CPL materials. Furthermore, P/M-1 based UV-LED devices demonstrated outstanding light-emitting performance, including high color-purity, excellent stability, remarkable luminous brightness (74,591.94 cd m-2), and a high electroluminescence dissymmetry factor (glum) value of 3.6×10-2. This study offers a robust strategy for the design and development of high-performance CPL materials utilizing achiral molecular architectures.
{"title":"Efficient Circularly Polarized Luminescence from Mn-Br Hybrid Perovskite Assembled by Achiral Architectures","authors":"Lu Zhai, Jiayi Yuan, Jianyi Huang, Xue-Wei Pan, Li Wan, Weihua Ning, Xiao-Ming Ren","doi":"10.1002/anie.202425543","DOIUrl":"https://doi.org/10.1002/anie.202425543","url":null,"abstract":"Circularly polarized luminescence (CPL)-active materials have attracted considerable attention due to their potential applications in various advanced technological fields. CPL activity typically requires compounds that crystallize in noncentrosymmetric chiral space groups. Achieving noncentrosymmetric crystal structures using achiral molecular architectures is highly appealing but remains a significant challenge. Herein, we present a strategy for designing and synthesizing high-performance CPL materials via crystallization-driven self-assembly using achiral architectures. We successfully obtained Mn2+-based halide enantiomeric hybrids (P-1 and M-1), self-assembled from [MnBr4]2- anions and rotational symmetric [Pr-dabco]2+ cations (Pr-dabco2+ = 1-Propyl-1,4-diazabicyclo-[2.2.2]octan-1-ium), crystallizing in the chiral space group P212121. The single crystals of 1 exhibit exceptionally high CPL performance, with a luminescence dissymmetry factor |glum| and photoluminescence quantum yield (PLQY) up to 4.8×10-2 and 86.8%, respectively, thus a record-high figure of merit (FM) of 4.2×10-2 among reported Mn2+-based CPL materials. Furthermore, P/M-1 based UV-LED devices demonstrated outstanding light-emitting performance, including high color-purity, excellent stability, remarkable luminous brightness (74,591.94 cd m-2), and a high electroluminescence dissymmetry factor (glum) value of 3.6×10-2. This study offers a robust strategy for the design and development of high-performance CPL materials utilizing achiral molecular architectures.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"20 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143654014","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Libo Xiang, Junyi Wang, Niclas Knoblauch, Alexander Matler, Qing Ye
The ortho-carboranyl carbophosphinocarbene (CPC) has been synthesized through a click-type reaction between the super strained carborane-fused borirane 1,2-BN(SiMe3)2-1,2-C2B10H10 and Bestmann ylide Ph3PCCO. The [Cl(CO)2Ir-CPC] and [Cl3Ga-CPC] complexes were synthesized, allowing the measurement of their Tolman electronic parameter (TEP) and the sum of Cl-Ga-Cl bond angles (∑ClGaCl), respectively. These data highlight their remarkable electron-donating ability. Further insights into its electron donating properties were gained through theoretical calculations, including analysis of frontier orbitals and proton affinity (PA). Preliminary reactivity investigations demonstrate that the new CPC readily forms adducts with boranes and can effectively stabilize borenium cations. Its strong nucleophilicity enables reactions with carbon dioxide, while its exceptional Brønsted basicity allows it to deprotonate imidazolium to generate carbene species.
{"title":"Conversion of Bestmann Ylide into Carbophosphinocarbene","authors":"Libo Xiang, Junyi Wang, Niclas Knoblauch, Alexander Matler, Qing Ye","doi":"10.1002/anie.202501955","DOIUrl":"https://doi.org/10.1002/anie.202501955","url":null,"abstract":"The ortho-carboranyl carbophosphinocarbene (CPC) has been synthesized through a click-type reaction between the super strained carborane-fused borirane 1,2-BN(SiMe3)2-1,2-C2B10H10 and Bestmann ylide Ph3PCCO. The [Cl(CO)2Ir-CPC] and [Cl3Ga-CPC] complexes were synthesized, allowing the measurement of their Tolman electronic parameter (TEP) and the sum of Cl-Ga-Cl bond angles (∑ClGaCl), respectively. These data highlight their remarkable electron-donating ability. Further insights into its electron donating properties were gained through theoretical calculations, including analysis of frontier orbitals and proton affinity (PA). Preliminary reactivity investigations demonstrate that the new CPC readily forms adducts with boranes and can effectively stabilize borenium cations. Its strong nucleophilicity enables reactions with carbon dioxide, while its exceptional Brønsted basicity allows it to deprotonate imidazolium to generate carbene species.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"33 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143654017","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Aoqi Yang, Xiang Gao, Maojun Pei, Jiacong Zhou, Honggang Wang, Can Liao, Wei Yan, Jianhua Xiao, Yao Liu, Jiujun Zhang
Passivation of magnesium (Mg) anode in the chloride‐free magnesium bis(trifluoromethanesulfonyl)imide (Mg(TFSI)2) electrolyte is a key challenge for Mg metal batteries. Tailoring solvation structure and solid electrolyte interphase (SEI) has been considered an effective strategy. Herein, a series of imidazole co‐solvents with different branched‐chain structures (methyl, ethyl and propyl) are introduced into the Mg(TFSI)2‐ether electrolyte to address the passivation issue. The ion‐solvent interaction, interfacial adsorption effect and SEI formation are comprehensively studied by theoretical calculations and experimental characterizations. Through molecular structure analysis, the long‐chain 1‐propylimidazole (PrIm) exhibits a strong coordination ability to Mg2+ and a favorable parallel adsorption configuration on the Mg surface. As a result, PrIm co‐solvent can not only restructure the solvation sheath of Mg2+, but also act as a dynamic protective shield to repel a part of TFSI‐ and 1,2‐dimethoxyethane (DME) away from the Mg surface. Benefited from the synergistic regulation effect of interfacial chemistry and ion‐solvent interactions, the chloride‐free Mg(TFSI)2‐DME+PrIm electrolyte ensures a minimal interface passivation and achieves highly reversible Mg plating/stripping. This work provides a guiding strategy for solvation structure regulation and interface engineering for rechargeable Mg metal battery.
{"title":"Synergistic Effects of Interfacial Chemistry and Ion‐Solvent Interactions to Enable Reversible Magnesium Metal Anode in Chloride‐Free Mg(TFSI)2 Electrolytes","authors":"Aoqi Yang, Xiang Gao, Maojun Pei, Jiacong Zhou, Honggang Wang, Can Liao, Wei Yan, Jianhua Xiao, Yao Liu, Jiujun Zhang","doi":"10.1002/anie.202424237","DOIUrl":"https://doi.org/10.1002/anie.202424237","url":null,"abstract":"Passivation of magnesium (Mg) anode in the chloride‐free magnesium bis(trifluoromethanesulfonyl)imide (Mg(TFSI)2) electrolyte is a key challenge for Mg metal batteries. Tailoring solvation structure and solid electrolyte interphase (SEI) has been considered an effective strategy. Herein, a series of imidazole co‐solvents with different branched‐chain structures (methyl, ethyl and propyl) are introduced into the Mg(TFSI)2‐ether electrolyte to address the passivation issue. The ion‐solvent interaction, interfacial adsorption effect and SEI formation are comprehensively studied by theoretical calculations and experimental characterizations. Through molecular structure analysis, the long‐chain 1‐propylimidazole (PrIm) exhibits a strong coordination ability to Mg2+ and a favorable parallel adsorption configuration on the Mg surface. As a result, PrIm co‐solvent can not only restructure the solvation sheath of Mg2+, but also act as a dynamic protective shield to repel a part of TFSI‐ and 1,2‐dimethoxyethane (DME) away from the Mg surface. Benefited from the synergistic regulation effect of interfacial chemistry and ion‐solvent interactions, the chloride‐free Mg(TFSI)2‐DME+PrIm electrolyte ensures a minimal interface passivation and achieves highly reversible Mg plating/stripping. This work provides a guiding strategy for solvation structure regulation and interface engineering for rechargeable Mg metal battery.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"9 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143653491","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Kauzmann paradox suggests that deeply supercooled liquids can have a lower entropy than the corresponding crystalline solids. While this entropy catastrophe has been thoroughly studied via equilibrium thermodynamics, the solidification process occurs far-from-equilibrium. By analyzing this process experimentally and theoretically, we show that surface speciation in core-shell particles can perturb the entropy production to an extent that a continuum equilibrium phase transition is not possible. Speciation of the surface causes divergence of associated stress vectors that generate nonequilibrium fluxes and frustrates homogeneous nucleation hence deep undercooling. The asymmetry of the speciation-derived surface tensor skews the minimum entropy production criterion. We analyze a set of nonequilibrium models, one showing and one averting the entropy catastrophe. Applying thermodynamic speed limits to these models, we show that the Kauzmann paradox takes another form. Deviations from the speed limit diverges the configurational entropy of the glass, but adding an interfacial state avoids the entropy catastrophe with significantly large supercooling.
{"title":"Avoiding the Kauzmann Paradox via Interface-Driven Divergence in States","authors":"Andrew Martin, Jason R. Green, Martin M. Thuo","doi":"10.1002/anie.202502197","DOIUrl":"https://doi.org/10.1002/anie.202502197","url":null,"abstract":"Kauzmann paradox suggests that deeply supercooled liquids can have a lower entropy than the corresponding crystalline solids. While this entropy catastrophe has been thoroughly studied via equilibrium thermodynamics, the solidification process occurs far-from-equilibrium. By analyzing this process experimentally and theoretically, we show that surface speciation in core-shell particles can perturb the entropy production to an extent that a continuum equilibrium phase transition is not possible. Speciation of the surface causes divergence of associated stress vectors that generate nonequilibrium fluxes and frustrates homogeneous nucleation hence deep undercooling. The asymmetry of the speciation-derived surface tensor skews the minimum entropy production criterion. We analyze a set of nonequilibrium models, one showing and one averting the entropy catastrophe. Applying thermodynamic speed limits to these models, we show that the Kauzmann paradox takes another form. Deviations from the speed limit diverges the configurational entropy of the glass, but adding an interfacial state avoids the entropy catastrophe with significantly large supercooling.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"20 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143660762","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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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