Pub Date : 2025-04-17DOI: 10.1016/j.chempr.2025.102573
Yu Hu, Mengxi Zhang, Han Xiao
The biosynthesis of bioorthogonal chemical handles for precise protein labeling remains a significant challenge. In this issue of Chem, Thomas Huber and colleagues report the successful biosynthesis of nitrile-containing amino acids and their site-specific incorporation into proteins, enabling efficient protein conjugation and fluorogenic labeling.
{"title":"Biosynthesis of nitrile-containing amino acids for rapid protein conjugation and fluorogenic labeling","authors":"Yu Hu, Mengxi Zhang, Han Xiao","doi":"10.1016/j.chempr.2025.102573","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102573","url":null,"abstract":"The biosynthesis of bioorthogonal chemical handles for precise protein labeling remains a significant challenge. In this issue of <em>Chem</em>, Thomas Huber and colleagues report the successful biosynthesis of nitrile-containing amino acids and their site-specific incorporation into proteins, enabling efficient protein conjugation and fluorogenic labeling.","PeriodicalId":268,"journal":{"name":"Chem","volume":"108 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143841942","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}
Pub Date : 2025-04-16DOI: 10.1016/j.chempr.2025.102542
Runda Li, Libing Yao, Jingyi Sun, Zengyi Sun, Kai Zhang, Jingjing Xue, Rui Wang
With rapid technological advancements, perovskite photovoltaics are approaching the final stage of commercialization. However, challenges arise due to differences between the fabrication processes for large-scale perovskite solar modules (PSMs) and laboratory-scale perovskite solar cells (PSCs). In this perspective, we highlight key obstacles in the transition from PSCs to PSMs across three main fabrication stages: precursor solution preparation, large-scale perovskite deposition, and post-treatment procedures for modules. Beyond addressing long-term stability, we emphasize critical yet often overlooked factors: reproducibility, cost, quality control, and sustainability in PSM manufacture. Finally, we provide our outlook by posing three controversial questions: which type of PSMs will be finally commercialized, how to balance the device area and lateral resistance, and how to realize a stable supply of raw materials. We hope that this effort may provide insights into targeted scientific strategies that can bridge these gaps and facilitate the commercialization of perovskite photovoltaics.
{"title":"Challenges and perspectives for the perovskite module research","authors":"Runda Li, Libing Yao, Jingyi Sun, Zengyi Sun, Kai Zhang, Jingjing Xue, Rui Wang","doi":"10.1016/j.chempr.2025.102542","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102542","url":null,"abstract":"With rapid technological advancements, perovskite photovoltaics are approaching the final stage of commercialization. However, challenges arise due to differences between the fabrication processes for large-scale perovskite solar modules (PSMs) and laboratory-scale perovskite solar cells (PSCs). In this perspective, we highlight key obstacles in the transition from PSCs to PSMs across three main fabrication stages: precursor solution preparation, large-scale perovskite deposition, and post-treatment procedures for modules. Beyond addressing long-term stability, we emphasize critical yet often overlooked factors: reproducibility, cost, quality control, and sustainability in PSM manufacture. Finally, we provide our outlook by posing three controversial questions: which type of PSMs will be finally commercialized, how to balance the device area and lateral resistance, and how to realize a stable supply of raw materials. We hope that this effort may provide insights into targeted scientific strategies that can bridge these gaps and facilitate the commercialization of perovskite photovoltaics.","PeriodicalId":268,"journal":{"name":"Chem","volume":"3 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143837101","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}
Pub Date : 2025-04-16DOI: 10.1016/j.chempr.2025.102543
Mark E. Carrington, Loh Min Yi, Erlendur Jónsson, Clare P. Grey
Aqueous organic flow batteries are a promising technology class for long-duration energy storage. However, the poor stability of redox-active components under the conditions frequently used in these batteries, coupled with the inherently high degree of active material chemical complexity, frequently gives rise to intricate degradation pathways that both limit attainable cycle life and are challenging to probe experimentally. Here, we utilize solution pH and bulk magnetic susceptibility to monitor the native minor equilibrium side reaction between water and the one-electron oxidized state of 2,2,6,6-tetramethyl-4-hydroxy-piperidin-1-oxyl (4-hydroxy-TEMPO)—an archetypical flow battery catholyte. This side reaction readily reports on both the main redox reaction of 4-hydroxy-TEMPO, which itself is not proton coupled, as well as on its principal self-discharge pathway. In so doing, it provides accurate, low-cost, and sensitive experimental insights into battery state of charge, state of health, and operating conditions for both flow and hybrid flow configurations.
{"title":"Practical flow battery diagnostics enabled by chemically mediated monitoring","authors":"Mark E. Carrington, Loh Min Yi, Erlendur Jónsson, Clare P. Grey","doi":"10.1016/j.chempr.2025.102543","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102543","url":null,"abstract":"Aqueous organic flow batteries are a promising technology class for long-duration energy storage. However, the poor stability of redox-active components under the conditions frequently used in these batteries, coupled with the inherently high degree of active material chemical complexity, frequently gives rise to intricate degradation pathways that both limit attainable cycle life and are challenging to probe experimentally. Here, we utilize solution pH and bulk magnetic susceptibility to monitor the native minor equilibrium side reaction between water and the one-electron oxidized state of 2,2,6,6-tetramethyl-4-hydroxy-piperidin-1-oxyl (4-hydroxy-TEMPO)—an archetypical flow battery catholyte. This side reaction readily reports on both the main redox reaction of 4-hydroxy-TEMPO, which itself is not proton coupled, as well as on its principal self-discharge pathway. In so doing, it provides accurate, low-cost, and sensitive experimental insights into battery state of charge, state of health, and operating conditions for both flow and hybrid flow configurations.","PeriodicalId":268,"journal":{"name":"Chem","volume":"55 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143837102","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}
One-dimensional (1D) halide perovskite quantum ribbons, featuring 1D corner-sharing octahedral networks, are promising for optoelectronics and photonics due to quantum confinement in two dimensions. However, the rational design of 1D perovskites remains challenging, and existing materials with narrow ribbon widths predominantly form self-trapped excitons, which limit their potential applications. Here, we synthesize 30 1D perovskites with controllable ribbon widths and edge octahedra terminations by organic cation engineering. We observe the absence of self-trapped excitons as the ribbon width increases up to four octahedra, alongside the ability to modulate their optoelectronic properties by tailoring the edge terminations. The 1D free excitons result in in-plane anisotropic photoluminescence (PL) emission with polarization degree reaching 60%. Moreover, we observe robust exciton-photon coupling with Rabi splitting energies up to 800 meV, which is significantly larger than those of three-dimensional (3D) and two-dimensional (2D) perovskites, demonstrating a class of 1D quantum materials for advanced optoelectronics and photonics.
{"title":"One-dimensional lead halide perovskite quantum ribbons with controllable edge terminations and ribbon widths","authors":"Xiaofan Jiang, Mingyuan Li, Yu Tao, Meng Zhang, Xinyu Li, Tianhao Zhang, Jiazhen Gu, Guangsheng Bai, Nanlong Zheng, Xuan Zhao, Huilong Hong, Leyang Jin, Xu Huang, Sanli Xu, Yan Guan, Chen Li, Wenkai Zhang, Yongping Fu","doi":"10.1016/j.chempr.2025.102548","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102548","url":null,"abstract":"One-dimensional (1D) halide perovskite quantum ribbons, featuring 1D corner-sharing octahedral networks, are promising for optoelectronics and photonics due to quantum confinement in two dimensions. However, the rational design of 1D perovskites remains challenging, and existing materials with narrow ribbon widths predominantly form self-trapped excitons, which limit their potential applications. Here, we synthesize 30 1D perovskites with controllable ribbon widths and edge octahedra terminations by organic cation engineering. We observe the absence of self-trapped excitons as the ribbon width increases up to four octahedra, alongside the ability to modulate their optoelectronic properties by tailoring the edge terminations. The 1D free excitons result in in-plane anisotropic photoluminescence (PL) emission with polarization degree reaching 60%. Moreover, we observe robust exciton-photon coupling with Rabi splitting energies up to 800 meV, which is significantly larger than those of three-dimensional (3D) and two-dimensional (2D) perovskites, demonstrating a class of 1D quantum materials for advanced optoelectronics and photonics.","PeriodicalId":268,"journal":{"name":"Chem","volume":"136 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143832147","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}
Pub Date : 2025-04-11DOI: 10.1016/j.chempr.2025.102541
Yosi Kratish, Yiqi Liu, Jiaqi Li, Anusheela Das, Leighton O. Jones, Amol Agarwal, Qing Ma, Michael J. Bedzyk, George C. Schatz, Takayuki Nakamuro, Eiichi Nakamura, Tobin J. Marks
Heterogeneous catalysts dominate the chemical industry but, unlike homogeneous catalysts, typically feature diverse, incompletely defined active sites. Thus, describing their structure-activity relationships remains challenging. In contrast, molecularly defined single-site heterogeneous catalysts (SSHCs) are poised to address these challenges and provide new avenues for catalysis research and development. The present study explores eco-friendly H2 production mediated by discrete MoO2 sites supported on carbon nanohorns (CNHs) and active for alcohol dehydrogenation. Although informative, detailed extended X-ray absorption fine structure (EXAFS), X-ray absorption near-edge structure (XANES), X-ray photoelectron spectroscopy (XPS,) kinetic measurements, and density functional theory (DFT) analysis alone cannot provide a full molecular picture of the reaction pathway. Here, using single-molecule atomic-resolution time-resolved electron microscopy (SMART-EM), we propose the identification of four key catalytic intermediates anchored to CNHs and uncover a new reaction pathway involving alkoxide/hemiacetal equilibration and acetal oligomerization. These intermediates are inferred through a combination of theory and SMART-EM, showcasing the potential of SMART-EM as a complementary tool for exploring mechanistic hypotheses in catalysis.
{"title":"Atomic-resolution imaging as a mechanistic tool for studying single-site heterogeneous catalysis","authors":"Yosi Kratish, Yiqi Liu, Jiaqi Li, Anusheela Das, Leighton O. Jones, Amol Agarwal, Qing Ma, Michael J. Bedzyk, George C. Schatz, Takayuki Nakamuro, Eiichi Nakamura, Tobin J. Marks","doi":"10.1016/j.chempr.2025.102541","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102541","url":null,"abstract":"Heterogeneous catalysts dominate the chemical industry but, unlike homogeneous catalysts, typically feature diverse, incompletely defined active sites. Thus, describing their structure-activity relationships remains challenging. In contrast, molecularly defined single-site heterogeneous catalysts (SSHCs) are poised to address these challenges and provide new avenues for catalysis research and development. The present study explores eco-friendly H<sub>2</sub> production mediated by discrete MoO<sub>2</sub> sites supported on carbon nanohorns (CNHs) and active for alcohol dehydrogenation. Although informative, detailed extended X-ray absorption fine structure (EXAFS), X-ray absorption near-edge structure (XANES), X-ray photoelectron spectroscopy (XPS,) kinetic measurements, and density functional theory (DFT) analysis alone cannot provide a full molecular picture of the reaction pathway. Here, using single-molecule atomic-resolution time-resolved electron microscopy (SMART-EM), we propose the identification of four key catalytic intermediates anchored to CNHs and uncover a new reaction pathway involving alkoxide/hemiacetal equilibration and acetal oligomerization. These intermediates are inferred through a combination of theory and SMART-EM, showcasing the potential of SMART-EM as a complementary tool for exploring mechanistic hypotheses in catalysis.","PeriodicalId":268,"journal":{"name":"Chem","volume":"108 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143820116","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}
Pub Date : 2025-04-11DOI: 10.1016/j.chempr.2024.102405
Hongchen Yang, Xiangwen Liu, Dingsheng Wang
In heterogeneous hydrogenation catalytic reactions, it is challenging to only hydrogenate the target functional group while preserving all other unsaturated bonds. In this issue of Chem, Shen and coworkers reported a Pt-Fe-Pt heterotrimer with densely populated and precisely arranged Pt atoms, which achieved an increased reaction rate and preferential hydrogenation of the C═O bond in crotonaldehyde catalytic properties.
{"title":"Circumventing the activity-selectivity trade-off: Pt-Fe-Pt active sites for selective heterogeneous hydrogenation of crotonaldehyde","authors":"Hongchen Yang, Xiangwen Liu, Dingsheng Wang","doi":"10.1016/j.chempr.2024.102405","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.102405","url":null,"abstract":"In heterogeneous hydrogenation catalytic reactions, it is challenging to only hydrogenate the target functional group while preserving all other unsaturated bonds. In this issue of <em>Chem</em>, Shen and coworkers reported a Pt-Fe-Pt heterotrimer with densely populated and precisely arranged Pt atoms, which achieved an increased reaction rate and preferential hydrogenation of the C═O bond in crotonaldehyde catalytic properties.","PeriodicalId":268,"journal":{"name":"Chem","volume":"99 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143820036","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}
Pub Date : 2025-04-10DOI: 10.1016/j.chempr.2024.11.003
Jiaxuan Wang , Daokuan Li , Xiaona Li , Guoquan Liu , Yong Zhu , Licheng Sun , Fei Li
In artificial photosynthesis, molecule/semiconductor hybrids combine the merits of the high activity of molecular catalysts and the high stability of semiconductor light absorbers. We report here a host-guest strategy for hybrid photoanode fabrication, where phosphonate-derivatized cyclodextrins (p-CDs) as hosts were anchored on the surface of a tungsten oxide (WO3) film, and molecular catalysts as guests were self-encapsulated into the cavities of p-CDs in either aqueous or organic media. By choosing an admantanyl cobaloxime complex (Co1) as a molecular water oxidation catalyst, the resulting WO3|p-CD|Co1 photoanode exhibited high photoelectrochemical (PEC) activity and stability for water oxidation due to the unexpected efficient charge separation and the strong affinity between p-CD and catalyst. In addition, the WO3|p-CD was identified to be a versatile platform for catalyst loading, when a 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) derivative was employed as the guest molecule, the conversion yield of PEC alcohol oxidation to aldehyde was dramatically increased.
{"title":"Hybrid photoanodes based on surface-bound host-guest molecular assemblies","authors":"Jiaxuan Wang , Daokuan Li , Xiaona Li , Guoquan Liu , Yong Zhu , Licheng Sun , Fei Li","doi":"10.1016/j.chempr.2024.11.003","DOIUrl":"10.1016/j.chempr.2024.11.003","url":null,"abstract":"<div><div>In artificial photosynthesis, molecule/semiconductor hybrids combine the merits of the high activity of molecular catalysts and the high stability of semiconductor light absorbers. We report here a host-guest strategy for hybrid photoanode fabrication, where phosphonate-derivatized cyclodextrins (p-CDs) as hosts were anchored on the surface of a tungsten oxide (WO<sub>3</sub>) film, and molecular catalysts as guests were self-encapsulated into the cavities of p-CDs in either aqueous or organic media. By choosing an admantanyl cobaloxime complex (<strong>Co1</strong>) as a molecular water oxidation catalyst, the resulting WO<sub>3</sub>|p-CD|<strong>Co1</strong> photoanode exhibited high photoelectrochemical (PEC) activity and stability for water oxidation due to the unexpected efficient charge separation and the strong affinity between p-CD and catalyst. In addition, the WO<sub>3</sub>|p-CD was identified to be a versatile platform for catalyst loading, when a 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) derivative was employed as the guest molecule, the conversion yield of PEC alcohol oxidation to aldehyde was dramatically increased.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 4","pages":"Article 102365"},"PeriodicalIF":19.1,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142793789","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}
Pub Date : 2025-04-10DOI: 10.1016/j.chempr.2024.11.019
Na Chen , Jing Xi , Tianpei He , Ruichen Shen , Rui Zhao , Haoming Chi , Jia Yao , Na Du , Lilei Yu , Yun Zhang , Tianyou Peng , Tiangang Liu , Quan Yuan
Inspired by the solar energy storage process during photosynthesis, we report herein a solar-decoupled photosynthetic biohybrid strategy through integrating a persistent photocatalyst with photoautotrophic microbes for sustainable and all-weather biomanufacturing, allowing for overcoming the intrinsic intermittent nature of solar energy availability by introducing energy storage and release processes. The results demonstrate that the apparent photo conversion efficiency (APCE) for of the persistent catalyst/R. palustris hybrid system reaches 8.30%, much higher than the 4.36% observed in bare R. palustris. Additionally, the proposed solar-decoupled biohybrid strategy not only shows considerable potential in coupling the practical power plant for the capture and utilization of CO2 from the flue gas but also exhibits universal applicability in different photosynthetic microorganisms. This concept-proving research offers new ideas to extend photocatalysis reactions without in situ irradiation and could pave new ways for sustainable solar energy utilization as well as biomanufacturing in space, where solar energy might be limited.
{"title":"Beyond natural synthesis via solar-decoupled biohybrid photosynthetic system","authors":"Na Chen , Jing Xi , Tianpei He , Ruichen Shen , Rui Zhao , Haoming Chi , Jia Yao , Na Du , Lilei Yu , Yun Zhang , Tianyou Peng , Tiangang Liu , Quan Yuan","doi":"10.1016/j.chempr.2024.11.019","DOIUrl":"10.1016/j.chempr.2024.11.019","url":null,"abstract":"<div><div>Inspired by the solar energy storage process during photosynthesis, we report herein a solar-decoupled photosynthetic biohybrid strategy through integrating a persistent photocatalyst with photoautotrophic microbes for sustainable and all-weather biomanufacturing, allowing for overcoming the intrinsic intermittent nature of solar energy availability by introducing energy storage and release processes. The results demonstrate that the apparent photo conversion efficiency (APCE) for of the persistent catalyst/<em>R</em>. <em>palustris</em> hybrid system reaches 8.30%, much higher than the 4.36% observed in bare <em>R. palustris</em>. Additionally, the proposed solar-decoupled biohybrid strategy not only shows considerable potential in coupling the practical power plant for the capture and utilization of CO<sub>2</sub> from the flue gas but also exhibits universal applicability in different photosynthetic microorganisms. This concept-proving research offers new ideas to extend photocatalysis reactions without <em>in situ</em> irradiation and could pave new ways for sustainable solar energy utilization as well as biomanufacturing in space, where solar energy might be limited.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 4","pages":"Article 102381"},"PeriodicalIF":19.1,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142917917","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}
Pub Date : 2025-04-10DOI: 10.1016/j.chempr.2025.102524
Yoshio Barrera , Florian F. Mulks
Houk, Garg, and colleagues report in Nature a new and intriguing synthetic method for coupling strained cyclic allenes and bicyclo[1.1.0]butanes through σ-bond insertion along a diradical pathway under mild conditions and ambient temperature. Geometric distortion induces diradical behavior, driving the reaction. This study enables the direct synthesis of functionalized bicyclo[2.1.1]hexanes, opening new avenues in drug discovery.
{"title":"Strained diradicaloids for σ-bond-insertion reactions: A breakthrough in drug discovery","authors":"Yoshio Barrera , Florian F. Mulks","doi":"10.1016/j.chempr.2025.102524","DOIUrl":"10.1016/j.chempr.2025.102524","url":null,"abstract":"<div><div>Houk, Garg, and colleagues report in <em>Nature</em> a new and intriguing synthetic method for coupling strained cyclic allenes and bicyclo[1.1.0]butanes through <strong><em>σ</em></strong>-bond insertion along a diradical pathway under mild conditions and ambient temperature. Geometric distortion induces diradical behavior, driving the reaction. This study enables the direct synthesis of functionalized bicyclo[2.1.1]hexanes, opening new avenues in drug discovery.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 4","pages":"Article 102524"},"PeriodicalIF":19.1,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143654260","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}
Pub Date : 2025-04-10DOI: 10.1016/j.chempr.2024.10.016
Till L. Kalkuhl , Israel Fernández , Terrance J. Hadlington
The discovery of unique mechanisms in 3d metal catalysis is of paramount importance in utilizing these Earth-abundant metals in place of scarce precious metals. Inspired by the Horiuti-Polanyi mechanism at play in heterogeneous hydrogenation catalysts, we describe a bimetallic molecular catalyst that can selectively semi-hydrogenate alkynes via a ligand-to-substrate hydride transfer mechanism. This mimics established heterogeneous mechanisms in which remote surface-bound hydride ligands undergo a similar reactive process. This is achieved through the development of a chelate-constrained gallium(I) ligand, which operates in concert with nickel(0) to (reversibly) cleave H2, generating a [GaNi] 1,2-dihydride complex that is found to be the resting state in the catalytic process. This discovery takes steps toward utilizing non-innocent low-valent group 13 centers in effective cooperative catalysis, opening new mechanistic pathways that may aid in employing Earth-abundant metals in key catalytic transformations.
发现 3d 金属催化的独特机制对于利用这些地球上丰富的金属来替代稀缺的贵金属至关重要。受异相氢化催化剂中 Horiuti-Polanyi 机制的启发，我们描述了一种双金属分子催化剂，它可以通过配体到底物的氢化物转移机制选择性地半氢化炔烃。这模仿了已建立的异质机制，其中远距离表面结合的氢化物配体也经历了类似的反应过程。这是通过开发一种受螯合物约束的镓（I）配体实现的，该配体与镍（0）协同（可逆地）裂解 H2，生成[GaNi] 1,2-二酸酐复合物，该复合物被发现是催化过程中的静止状态。这一发现为利用非无辜的低价 13 族中心进行有效的合作催化迈出了一步，开辟了新的机理途径，可能有助于在关键的催化转化过程中使用地球上富集的金属。
{"title":"Cooperative hydrogenation catalysis at a constrained gallylene-nickel(0) interface","authors":"Till L. Kalkuhl , Israel Fernández , Terrance J. Hadlington","doi":"10.1016/j.chempr.2024.10.016","DOIUrl":"10.1016/j.chempr.2024.10.016","url":null,"abstract":"<div><div>The discovery of unique mechanisms in 3<em>d</em> metal catalysis is of paramount importance in utilizing these Earth-abundant metals in place of scarce precious metals. Inspired by the Horiuti-Polanyi mechanism at play in heterogeneous hydrogenation catalysts, we describe a bimetallic molecular catalyst that can selectively semi-hydrogenate alkynes via a ligand-to-substrate hydride transfer mechanism. This mimics established heterogeneous mechanisms in which remote surface-bound hydride ligands undergo a similar reactive process. This is achieved through the development of a chelate-constrained gallium(I) ligand, which operates in concert with nickel(0) to (reversibly) cleave H<sub>2</sub>, generating a [GaNi] 1,2-dihydride complex that is found to be the resting state in the catalytic process. This discovery takes steps toward utilizing non-innocent low-valent group 13 centers in effective cooperative catalysis, opening new mechanistic pathways that may aid in employing Earth-abundant metals in key catalytic transformations.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 4","pages":"Article 102349"},"PeriodicalIF":19.1,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142601923","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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