Journal of the American Chemical Society最新文献_第4页

Intermolecular N-N Coupling of a Dinitrosyl Iron Complex Induced by Hydrogen Bond Donors in the Secondary Coordination Sphere.

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2025-02-19 DOI: 10.1021/jacs.4c12787

Kayla M Fugami, Gabriel S Black, Tim Kowalczyk, Takele Seda, John D Gilbertson

引用次数: 0

Irreversible Deactivation Pathways in Ni(II)-Catalyzed Nonalternating Ethylene-Carbon Monoxide Copolymerization.

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2025-02-19 DOI: 10.1021/jacs.4c16468

Lukas Odenwald, Lukas Wursthorn, Stefan Mecking

引用次数: 0

Promoting C-F Bond Activation for Perfluorinated Compounds Decomposition via Atomically Synergistic Lewis and Brønsted Acid Sites.

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2025-02-19 DOI: 10.1021/jacs.4c15280

Wenjie Luo, Kang Liu, Tao Luo, Junwei Fu, Hang Zhang, Chao Ma, Ting-Shan Chan, Cheng-Wei Kao, Zhang Lin, Liyuan Chai, Michelle L Coote, Min Liu

{"title":"Promoting C-F Bond Activation for Perfluorinated Compounds Decomposition via Atomically Synergistic Lewis and Brønsted Acid Sites.","authors":"Wenjie Luo, Kang Liu, Tao Luo, Junwei Fu, Hang Zhang, Chao Ma, Ting-Shan Chan, Cheng-Wei Kao, Zhang Lin, Liyuan Chai, Michelle L Coote, Min Liu","doi":"10.1021/jacs.4c15280","DOIUrl":"https://doi.org/10.1021/jacs.4c15280","url":null,"abstract":"Catalytic hydrolysis is a sustainable method for the degradation of perfluorinated compounds (PFCs) but is challenged by the high reaction temperatures required to cleave strong C-F bonds. Herein, we developed an innovative C-F activation strategy by constructing synergistic Lewis and Brønsted acid pairs over atomically dispersed Zn-O-Al sites to promote C-F bond activation for decomposition of typical PFCs, CF4. Density functional theory (DFT) calculations demonstrate tricoordinated Al (AlIII) sites and Zn-OH functional, respectively, as Lewis and Brønsted acid sites over Zn-O-Al, synergistically enhancing the adsorption and decomposition of CF4. X-ray absorption spectroscopy (XAS), pyridine infrared spectroscopy (Py-IR), and ammonia temperature-programmed desorption (NH3-TPD) verified the presence of both AlIII and Zn-OH on the atomically dispersed Zn-O-Al sites. CF4-TPD and in situ infrared spectroscopy confirmed that the Zn-O-Al sites facilitate CF4 adsorption and C-F bond activation. As a result, the Zn-O-Al sites with synergistic Lewis and Brønsted acid pairs achieved 100% CF4 decomposition at a low temperature of 560 °C and demonstrated outstanding stability for more than 250 h.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":14.4,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143447313","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}

引用次数: 0

Machine-Learning-Accelerated Surface Exploration of Reconstructed BiVO₄(010) and Characterization of Their Aqueous Interfaces.

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2025-02-19 DOI: 10.1021/jacs.4c17739

Yonghyuk Lee, Taehun Lee

{"title":"Machine-Learning-Accelerated Surface Exploration of Reconstructed BiVO4(010) and Characterization of Their Aqueous Interfaces.","authors":"Yonghyuk Lee, Taehun Lee","doi":"10.1021/jacs.4c17739","DOIUrl":"https://doi.org/10.1021/jacs.4c17739","url":null,"abstract":"Understanding the semiconductor-electrolyte interface in photoelectrochemical (PEC) systems is crucial for optimizing the stability and reactivity. Despite the challenges in establishing reliable surface structure models during PEC cycles, this study explores the complex surface reconstructions of BiVO4(010) by employing a computational workflow integrated with a state-of-the-art active learning protocol for a machine-learning interatomic potential and global optimization techniques. Within this workflow, we identified 494 unique reconstructed surface structures that surpass conventional chemical intuition-driven, bulk-truncated models. After constructing the surface Pourbaix diagram under Bi- and V-rich electrolyte conditions using density functional theory and hybrid functional calculations, we proposed structural models for the experimentally observed Bi-rich BiVO4 surfaces. By performing hybrid functional molecular dynamics simulations with the explicit treatment of water molecules on selected reconstructed BiVO4(010) surfaces, we observed water dissociation from molecular water. Our findings demonstrate significant water dissociation on reconstructed Bi-rich surfaces, highlighting the critical role of bare and undercoordinated Bi sites (only observable in reconstructed surfaces) in driving hydration processes. Our work establishes a foundation for understanding the role of complex, reconstructed Bi surfaces in surface hydration and reactivity. Additionally, our theoretical framework for exploring surface structures and predicting reactivity in multicomponent oxides offers a precise approach to describing complex surface and interface processes in PEC systems.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":14.4,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143447307","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}

引用次数: 0

Differential Packing of Cs₂Mo₆Br₁₄ Cluster-Based Halide in Variable Diameter Carbon Nanotubes with Elimination and Polymerization to 1D [Mo₂Br₆]_x Ising Model Structures by Steric Confinement.

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2025-02-19 DOI: 10.1021/jacs.4c14883

Eric Faulques, Victor G Ivanov, Stéphane Cordier, Reza J Kashtiban, Yann Molard, Jean-Luc Duvail, Nataliya Kalashnyk, Jeremy Sloan

{"title":"Differential Packing of Cs2Mo6Br14 Cluster-Based Halide in Variable Diameter Carbon Nanotubes with Elimination and Polymerization to 1D [Mo2Br6]x Ising Model Structures by Steric Confinement.","authors":"Eric Faulques, Victor G Ivanov, Stéphane Cordier, Reza J Kashtiban, Yann Molard, Jean-Luc Duvail, Nataliya Kalashnyk, Jeremy Sloan","doi":"10.1021/jacs.4c14883","DOIUrl":"https://doi.org/10.1021/jacs.4c14883","url":null,"abstract":"We present detailed findings on the imaging, structure, and vibrational properties of novel hybrids of the red-emitting octahedral cluster-based compound Cs2Mo6Br14 encapsulated within single-walled carbon nanotubes (SWCNTs) of varying diameter. We explore the subtle relationship between the SWCNT internal diameter and Cs2Mo6Br14 cluster packing and find a hierarchical relationship between the nature of the cluster packing and a progressive tendency toward formation of one-dimensional (1D) structures as the SWCNT diameter narrows from 24 to 11 Å. As the internal SWCNT van der Waals radius approaches the outside diameter (OD) of the [{Mo6IIBr8i}Br6a]2- (more simplistically, [Mo6IIIBr14]2-) molecular anion species, SWCNT steric confinement causes a compositional elimination and polymerization resulting in the formation of reduced extended [Mo2IIIBr6]x nanoribbons which approximate 1D Ising model structures. Our experimental results, obtained through high-resolution transmission electron microscopy and Raman spectroscopy, are supplemented by density functional theory (DFT) calculations.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":14.4,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143447422","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}

引用次数: 0

Synthesis of Non-C₂-Symmetric Biaryldiols via Organo-Electro Catalyzed Aryl-Aryl Dehydrogenative Cross-Coupling.

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2025-02-19 DOI: 10.1021/jacs.4c16426

Dingguo Song, Weiwei Huang, Wenji Zhang, Changdi Zheng, Yuhua Chen, Jiayang Lv, Cunwei Zheng, Weihui Zhong, Fei Ling

引用次数: 0

Diastereomeric Configuration Drives an On-Surface Specific Rearrangement into Low Bandgap Non-Benzenoid Graphene Nanoribbons.

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2025-02-19 DOI: 10.1021/jacs.4c10478

Federico Villalobos, Jesús I Mendieta-Moreno, Jorge Lobo-Checa, Sara P Morcillo, José I Martínez, José María Gómez-Fernández, Pedro L de Andres, José A Martin-Gago, Juan M Cuerva, Araceli G Campaña, Carlos Sánchez-Sánchez

{"title":"Diastereomeric Configuration Drives an On-Surface Specific Rearrangement into Low Bandgap Non-Benzenoid Graphene Nanoribbons.","authors":"Federico Villalobos, Jesús I Mendieta-Moreno, Jorge Lobo-Checa, Sara P Morcillo, José I Martínez, José María Gómez-Fernández, Pedro L de Andres, José A Martin-Gago, Juan M Cuerva, Araceli G Campaña, Carlos Sánchez-Sánchez","doi":"10.1021/jacs.4c10478","DOIUrl":"https://doi.org/10.1021/jacs.4c10478","url":null,"abstract":"Stereochemistry, usually associated with the three-dimensional arrangement of atoms in molecules, is crucial in processes like life functions, drug action, or molecular reactions. This three-dimensionality typically originates from sp3 hybridization in organic molecules, but it is also present in out-of-plane sp2-based molecules as a consequence of helical structures, twisting processes, and/or the presence of nonbenzenoid rings, the latter significantly influencing their global stereochemistry and leading to the emergence of new exotic properties. In this sense, on-surface synthesis methodologies provide the perfect framework for the precise synthesis and characterization of organic systems at the atomic scale, allowing for the accurate assessment of the associated stereochemical effects. In this work, we demonstrate the importance of the initial diastereomeric configuration in the surface-induced skeletal rearrangement of a substituted cyclooctatetraene (COT) moiety-a historical landmark in the understanding of aromaticity-into a cyclopenta[c,d]azulene (CPA) one in a chevron-like graphene nanoribbon (GNR). These findings are evidenced by combining bond-resolved scanning tunneling microscopy with theoretical ab initio calculations. Interestingly, the major well-defined product, a CPA chevron-like GNR, exhibits the lowest bandgap reported to date for an all-carbon chevron-like GNR, as evidenced by scanning tunneling spectroscopy measurements. This work paves the way for the rational application of stereochemistry in the on-surface synthesis of novel graphene-based nanostructures.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":14.4,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143456257","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}

引用次数: 0

Bro̷nsted Acid-Catalyzed Reduction of Furans

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-02-19 DOI: 10.1021/jacs.4c18485

Nils Frank, Markus Leutzsch, Benjamin List

引用次数: 0

Enantioselective Alkyl-Acyl Radical Cross-Coupling Enabled by Metallaphotoredox Catalysis.

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2025-02-19 DOI: 10.1021/jacs.4c15275

Tao Li, Zhen Xu, Yongliang Huang, Weisai Zu, Haohua Huo

{"title":"Enantioselective Alkyl-Acyl Radical Cross-Coupling Enabled by Metallaphotoredox Catalysis.","authors":"Tao Li, Zhen Xu, Yongliang Huang, Weisai Zu, Haohua Huo","doi":"10.1021/jacs.4c15275","DOIUrl":"https://doi.org/10.1021/jacs.4c15275","url":null,"abstract":"Radical-radical cross-coupling (RCC) offers a promising approach for carbon-carbon bond formation in organic synthesis, particularly for creating complex, three-dimensional molecules. However, achieving both cross- and enantioselectivity in RCC reactions has remained a significant challenge. Here, we report a novel metallaphotoredox platform that enables highly enantioselective decarboxylative coupling of carboxylic acid derivatives with aldehydes. Our strategy leverages independent control over radical generation and subsequent enantioselective bond formation through fine-tuning of a common photocatalyst and a simple chiral bis(oxazoline) nickel catalyst. This redox-neutral protocol requires no exogenous oxidants or reductants and demonstrates broad substrate scope and functional group compatibility in the synthesis of enantioenriched α-aryl and α-amino ketones. The α-amino ketone products can be readily transformed into valuable β-amino alcohols, streamlining access to these important motifs. Furthermore, we showcase the potential of this approach for more challenging enantioselective C(sp3)-C(sp3) alkyl-alkyl RCC reactions. This unified platform for enantioselective alkyl-acyl radical cross-coupling represents a significant advance in asymmetric catalysis and underscores the potential for metallaphotoredox catalysis to exploit new mechanisms to solve long-standing synthetic problems.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":14.4,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143447284","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}

引用次数: 0

Correction to "Catalytic Asymmetric Transfer Hydrogenation of Acylboronates: BMIDA as the Privileged Directing Group".

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2025-02-19 DOI: 10.1021/jacs.5c02351

Xiangjian Meng, Shouang Lan, Ting Chen, Haotian Luo, Lixuan Zhu, Nanchu Chen, Jinggong Liu, Shuang Yang, Andrej Emanuel Cotman, Qi Zhang, Xinqiang Fang

引用次数: 0