Chemical Science最新文献

{"title":"Ligand non-innocence and an unusual σ-bond metathesis step enables catalytic borylation using 9-borabicyclo-[3.3.1]-nonane.","authors":"Milan Bisai, Justyna Losiewicz, Gary Stephen Nichol, Andrew Dominey, Stephen P. Thomas, Stuart Alan Macgregor, Michael James Ingleson","doi":"10.1039/d5sc02085a","DOIUrl":"https://doi.org/10.1039/d5sc02085a","url":null,"abstract":"The metal-catalyzed intermolecular C–H borylation of arenes is an extremely powerful C–H functionalization methodology. However, to date it is effectively restricted to forming organo-boronate esters (Aryl–B(OR)2) with its application to form other organoboranes rarely explored. Herein, we report a catalytic intermolecular heteroarene C–H borylation method using the commercial hydroborane 9-borabicyclo-[3.3.1]-nonane, (H–BBN)2. This process is effective for mono- and di-borylation to form a range of Heteroaryl–BBN compounds using either NacNacAl or NacNacZn ((NacNac={(2,6-iPr2C6H3)N(CH3)C}2CH) based catalysts. Notably, mechanistic studies indicated a highly unusual -bond metathesis process between NacNacZn–Aryl and the dimeric hydroborane, with first order kinetics in the hydroborane dimer ((H–BBN)2). Our calculated metathesis pathway involves ligand non-innocence and addition of both H–BBN units in (H–BBN)2 to the NacNacZn–Heteroaryl complex. This is in contrast to the conventional -bond metathesis mechanism using other hydroboranes which invariably proceeds by reaction of one equivalent of a monomeric hydroborane (e.g., H-B(OR)2) with a M–C unit. Overall, this work demonstrates the potential of extending catalytic arene C–H borylation beyond boronate esters, while highlighting that the σ-bond metathesis reaction can be mechanistically more complex when utilizing dimeric hydroboranes such as (H-BBN)2.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"3 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143832320","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}

{"title":"Carbene-catalyzed enantioselective construction of quasi-symmetrical spirocyclic hydroquinone with minor chiral distinction","authors":"Panlong Ren, Qing Zhao, Yonggui Robin Chi, Tingshun Zhu","doi":"10.1039/d5sc01605c","DOIUrl":"https://doi.org/10.1039/d5sc01605c","url":null,"abstract":"Constructing nearly symmetrical chiral center with tiny chiral differences is a challenging task in asymmetric synthesis. As a representative example, natural antibiotic Fredericamycin A (FDM-A) has a unique structure with quasi-symmetrical spirocyclic hydroquinone and remains difficult for chemical synthesis. Herein we developed an N-heterocyclic carbene-catalyzed enantioselective hydroquinone formation reaction, with desymmetrization of spirocyclic cyclopentene-1,3-diones to construct these challenging structures. With the help of our method, the asymmetric synthesis of FDM-A (require 26-step or 32-step synthesis) was shortened to 11 steps. Several analogs of FDM-A are readily available as well. Moreover, a more challenging all-carbon quaternary chiral center with minimal differences (H vs. D) in remote position (6 atoms away from the chiral center) was also constructed to investigate the performance of the extremely weak-chirality small molecule.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"16 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143832315","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}

{"title":"Establishing Stability Number Descriptor for Fe-N-C Fuel Cell Electrocatalysts","authors":"Yu-Ping Ku, Kavita Kumar, Antoine Bonnefont, Li Jiao, Marco Mazzucato, Christian Durante, Frederic Jaouen, Serhiy Cherevko","doi":"10.1039/d5sc00547g","DOIUrl":"https://doi.org/10.1039/d5sc00547g","url":null,"abstract":"Fe-N-C electrocatalysts demonstrate high potential in catalyzing oxygen reduction reaction (ORR) in polymer electrolyte fuel cells, yet the bottleneck for their application is their moderate stabilities. In our previous work, we discovered a linear correlation between the rates of ORR and Fe dissolution in alkaline media at room temperature, and the stability (S-) number descriptor that reflects this correlation was introduced. On the way toward further generalization and establishment of this descriptor, we investigate the effect of pH, potential, current density, and temperature on the dissolution behavior of various representative Fe-N-C electrocatalysts. It is shown that the S-number concept is also applicable for ORR and Fe dissolution in alkaline electrolytes at 70 ℃. It is more challenging to apply the S-number in acidic media, where the S-number is a function of ORR current density. A kinetic model is introduced, showing that the local pH inside the catalyst layer rises significantly with increasing current densities. The pH dependence of the S-number explains the results in acidic electrolytes. Accounting for such a dependence, the S-number descriptor can also benchmark Fe-N-C stability in acidic electrolytes. It is considered that this concept can also be extended to other reactions, allowing more rational activity and stability screening of electrocatalysts.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"39 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143827246","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}

{"title":"Intensive Near-Infrared Emitting Au7Cu10 Nanoclusters for Both Energy and Electron Harvesting","authors":"Wei Zhang, Tingting Xu, Jie Kong, Yuanming Li, Xiaoguo Zhou, Jiachen Zhang, Qun Zhang, Yongbo Song, Yi Luo, Meng Zhou","doi":"10.1039/d5sc00671f","DOIUrl":"https://doi.org/10.1039/d5sc00671f","url":null,"abstract":"Triplet excitons have gained increasing recognition as inherent characteristics of various nanomaterials. However, the practical application of triplet excitons is limited due to their confinement within the material where they originate, posing significant challenges to harnessing their potential. In this work, we report direct extraction of both triplet energy and electrons from newly synthesized atomically precise Au<small>₇</small>Cu<small>₁₀</small> nanoclusters (NCs). These NCs exhibit intensive near-infrared (NIR) emission with a quantum yield of 31% at room temperature. They also display near-unity quantum yield of intersystem crossing (ISC) with strong spin-orbit coupling (SOC) up to 864 cm<small>^-1</small>. Consequently, Au<small>₇</small>Cu<small>₁₀</small> NCs can act as triplet sensitizers, facilitating efficient triplet-triplet annihilation and achieving upconverted emission with an efficiency of 18.4% in perylene. Furthermore, rapid electron injection from Au<small>₇</small>Cu<small>₁₀</small> NCs in triplet state to methyl viologen was clearly observed. This study represents the first direct extraction of both triplet energy and electrons from same metal NCs, indicating their potential as molecular triplet energy and electron surrogates in optoelectronics, photocatalysis, and solar energy conversion.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"117 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143827248","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}

{"title":"Intramolecular Arylsulfide-Coordinated Diboraanthracenes: Effect of B–S Coordination on Ground-State and Excited-State Behavior","authors":"Hiroki Narita, Alexander Virovets, Hans-Wolfram Lerner, Matthias Wagner, Shigehiro Yamaguchi","doi":"10.1039/d5sc01726b","DOIUrl":"https://doi.org/10.1039/d5sc01726b","url":null,"abstract":"Controlling boron–heteroatom interactions in triarylborane scaffolds can lead to stimuli-responsive photophysical properties. A key molecular design to this end is the utilization of a labile coordination bond between the boron atom and a Lewis basic heteroatom. Herein, we report the synthesis of a series of 9,10-dihydro-9,10-diboraanthracenes (DBAs) bearing ortho-arylthiomethyl-substituted phenyl groups on the boron atom as a new family of stimuli-responsive boron-containing π-conjugated molecules. The two ortho-arylthiomethyl groups coordinate to the boron atoms by forming five-membered rings in the DBA scaffolds to produce the cis isomers predominantly, where the strength of the boron–sulfur bonds can be tuned by structural and electronic modifications of the aryl groups. In the ground state, the B–S bond is cleaved upon heating in solution. In the excited state, the B–S bond undergoes dissociation, resulting in emission from tricoordinate species. The aryl groups on the sulfur atom also play a role in forming an intramolecular charge- transfer state, whereby the emissions are bathochromically shifted with large apparent Stokes shifts. Moreover, the B–S bonds are sensitive to solvent polarity and temperature, resulting in multiple emission properties depending on the surrounding environment.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"120 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143827298","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}

{"title":"Potassium tert-butoxide Mediated Stereoselective/Direct Mannich Reaction of α-Substituted-γ-Lactams with in situ Generated Aryl N-Silyl Imines","authors":"Tyler D. Casselman, Mithun Madhusudhanan, Binh Khanh Mai, Peng Liu, Brian M. Stoltz","doi":"10.1039/d4sc06391k","DOIUrl":"https://doi.org/10.1039/d4sc06391k","url":null,"abstract":"A potassium <em>tert</em>-butoxide (KO<em>t</em>-Bu)-mediated Mannich reaction between α-substituted-γ-lactams and <em>N</em>-silyl imines is reported. <em>N</em>-silyl imines are generated <em>in situ </em>from readily available aryl nitriles and <em>directly </em>combined with the lactams, without preformation of the lactam enolate, to afford the α-quaternary center-bearing Mannich bases in high yield and with high diastereoselectivity (24 examples). This reaction is shown to be catalytic with respect to KO<em>t</em>-Bu and the catalytic mechanism has been investigated using density functional theory calculations. The computational investigations suggest that the diastereoselectivity is controlled by explicit interactions between a binuclear potassium complex and both the imine nitrogen and the enolate oxygen atoms in the selectivity-determining transition states. The Mannich products are shown to be useful in accessing novel spirocyclic pyrrolidines.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"66 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143827247","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}

{"title":"Tailored design of an oxygen-rich stable Co-MOF integrated with MXene nanofibers as an advanced heterostructure for high-performance ammonium-ion supercapacitors","authors":"Nissar Hussain, Shaikh M. Mobin","doi":"10.1039/d5sc00171d","DOIUrl":"https://doi.org/10.1039/d5sc00171d","url":null,"abstract":"Ammonium ions (NH<small>₄</small><small>⁺</small>) are promising non-metallic charge carriers for sustainable and cost-effective advanced electrochemical energy storage. However, the development of electrode materials with well-defined structural features to facilitate rapid NH<small>₄</small><small>⁺</small> diffusion kinetics remains a significant challenge. In this study, we demonstrate the design of a novel oxygen-rich cobalt-based metal–organic framework (Co-MOF) showcasing unique (O<small>₄</small>–CoN<small>₂</small>) coordination geometry. This distinctive structure of Co-MOF contributes to high stability, abundant active sites, and enhanced electrochemical performance. To further boost performance, Co-MOF nanoflowers were uniformly integrated with Ti<small>₃</small>C<small>₂</small>T<small>_<em>x</em></small> MXene carbonized nanofibers (MXCNF), forming advanced Co-MOF@MXCNF heterostructures. These heterostructures exhibit a highly porous, nanofibrous morphology, delivering a notable specific capacitance of 980 F g<small>⁻¹</small> at a current density of 1 A g<small>⁻¹</small> and excellent cycling stability, retaining 91.1% capacitance after 16 000 cycles. When paired with a porous MXCNF anode, the ammonium-ion hybrid supercapacitors (AIHSCs) delivered an impressive energy density of 41.5 mW h kg<small>⁻¹</small> with the corresponding power density of 800 mW kg<small>⁻¹</small>, retaining 87% of their capacitance after 16 000 cycles. This study highlights the synergistic advantages of integrating stable MOFs with MXene nanofibers for remarkable ammonium-ion storage. It establishes a framework for designing high-performance energy storage materials, paving the way for next-generation sustainable energy storage devices.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"38 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143827249","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}

{"title":"Coordination of Ethane, Pentane and Cyclopentane to a Cationic Osmium complex: Comparisons in Alkane Binding","authors":"James Duncan Watson, Dejan Mizdrak, Leslie D Field, Graham Edwin Ball","doi":"10.1039/d5sc00973a","DOIUrl":"https://doi.org/10.1039/d5sc00973a","url":null,"abstract":"When a solution of [<em>η</em><small>⁵</small>‑CpOs(CO)<small>₃</small>]<small>⁺</small>[Al(OC(CF<small>₃</small>)<small>₃</small>)<small>₄</small>]<small>^-</small> is photolyzed in the presence of ethane, pentane or cyclopentane, photo-liberation of carbon monoxide occurs and the corresponding metal-alkane s‑complex, [<em>η</em><small>⁵</small>‑CpOs(CO)<small>₂</small>(alkane)]<small>⁺</small> (where alkane = ethane, pentane and cyclopentane), forms. Here we report the NMR spectroscopic and computational investigations into the structure, reactivity, lifetimes and binding energies of the osmium-centred alkane <em>σ</em>‑complexes [<em>η</em><small>⁵</small>‑CpOs(CO)<small>₂</small>(C<small>₂</small>H<small>₆</small>)]<small>⁺</small>, [<em>η</em><small>⁵</small>‑CpOs(CO)<small>₂</small>(n‑C<small>₅</small>H<small>₁₂</small>)]<small>⁺</small> and [<em>η</em><small>⁵</small>‑CpOs(CO)<small>₂</small>(c‑C<small>₅</small>H<small>₁₀</small>)]<small>⁺</small>. The fragment [<em>η</em><small>⁵</small>‑CpOs(CO)<small>₂</small>]<small>⁺</small> binds alkanes tightly and forms remarkably stable complexes with ethane, n-pentane and cyclopentane. The effective half-life for [<em>η</em><small>⁵</small>-CpOs(CO)<small>₂</small>(n-C<small>₅</small>H<small>₁₂</small>)]<small>⁺</small> and [<em>η</em><small>⁵</small>-CpOs(CO)<small>₂</small>(c-C<small>₅</small>H<small>₁₀</small>)]<small>⁺</small> are 0.95 and 0.21 h at -50 <small>^o</small>C, making these amongst the most stable metal-alkane complexes in solution reported to date. Different isomers of the n-pentane complexes are observed and the relative amount of each in solution is strongly dependent on the presence of photo-irradiation. When irradiated, the methyl bound (C1) isomer is the major product and in the absence of irradiation the system equilibrates, and the methylene bound isomers (C2 and C3) are the major products.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"14 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143819193","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}

{"title":"Promotion or suppression on hydrogen evolution activity? The competition between sodium cation and quaternary ammonium ions at metal/water interface","authors":"Shilin Bo, Yang Xiang, Qiong Xiang, Li Li, Xun Huang, Zidong Wei","doi":"10.1039/d5sc01034a","DOIUrl":"https://doi.org/10.1039/d5sc01034a","url":null,"abstract":"Quaternary ammonium salts (QAS) are frequently utilized to modulate the structure of the cathodic electric double layer in processes such as water electrolysis and hydrogenation reactions. However, literature reports have shown that QAS can both suppress and promote hydrogen evolution activity, yet the underlying mechanisms remain incompletely understood. In this study, we experimentally observed that the presence of QAS alone accelerates hydrogen evolution compared to NaOH solutions. Conversely, when QAS is combined with Na+ or H+, it inhibits hydrogen evolution. Ab initio molecular dynamics simulation and surface-enhanced infrared absorption spectroscopy results indicate that Na+ ions disrupt the hydrogen bond network at the interface, leading to a disorder in the water chain arrangement. In contrast, QAS enhances the hydrogen bond network, thereby facilitating the hydrogen evolution reaction. However, coexistence of Na+ and QAS leads to hydration competition, creating gaps in the hydrogen bond network near the surface and impeding hydrogen transport. These findings enhance our understanding of QAS in hydrogen evolution and guide future interface modulation strategies.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"218 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143819195","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}

{"title":"The fellowship of the Grignard: 21th century computational tools for hundred years-old chemistry","authors":"Michele Cascella, Sigbjørn L. Bore, Odile Eisenstein","doi":"10.1039/d5sc01078k","DOIUrl":"https://doi.org/10.1039/d5sc01078k","url":null,"abstract":"This perspective begins with the discovery of the Grignard reaction by a graduate student in the last years of the 19th century, before describing why it has remained largely unexplained for more than a century. From the summary of what has been achieved, focusing on the computational aspects, it is now clear that further studies of the chemistry of any chemical species that is highly sensitive to solvents, such as Group I and II elements, require a holistic approach that includes the solute andthe solvent together. Ab initio molecular dynamics, which meets these requirements, has produced some results, but it hits hard limits due to its relatively heavy computational costs. In these days, it is becoming clear that data-driven methods, including machine learning potentials and simulations driven by quantitative on-the-fly calculation of relevant observables, have the potential to better and more completely explore the very large chemical space associated with the presence of a large number of species in solution. These methodologies have the chance to give the keys to enter into the challenging and still poorly explored world of chemical species whose behaviour and reactivity are strongly influenced by the solvent and the experimental conditions.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"13 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143819775","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}