Inorganic Chemistry Frontiers最新文献_第3页

Phosphonic, arsonic, stibonic, and bismuthonic acids: a unified perspective on a fragmented family of group 15 oxyacids 膦酸、砷酸、铋酸：对15组氧酸的一个破碎家族的统一观点

IF 7 1区化学

Inorganic Chemistry Frontiers Pub Date : 2026-11-03 DOI: 10.1039/d6qi01864e

Bi Youan E. Tra,Timothy C. Johnstone

{"title":"Phosphonic, arsonic, stibonic, and bismuthonic acids: a unified perspective on a fragmented family of group 15 oxyacids","authors":"Bi Youan E. Tra,Timothy C. Johnstone","doi":"10.1039/d6qi01864e","DOIUrl":"https://doi.org/10.1039/d6qi01864e","url":null,"abstract":"Organopnictonic acids are compounds with the general formula RPnO3H2 where Pn = P, As, Sb, Bi. They comprise a family of compounds with many useful properties and also provide a powerful framework for understanding fundamental periodic trends in bonding, structure, and reactivity across group 15. In this review, we present a comprehensive and critical perspective on phosphonic, arsonic, stibonic, and bismuthonic acids, covering the development of the field from its earliest foundations to the present day and, for the first time, unifying these oxyacids within a single conceptual framework. We describe the electronic and structural principles governing pnictogen–oxygen bonding, emphasizing the progressive attenuation of multiple bonding, and the growing propensity for hydrolysis, aggregation, and coordination sphere expansion on descending the group. The well-established chemistry of phosphonic and arsonic acids is treated concisely to enable direct comparison to the emerging experimental developments in the chemistry of stibonic and bismuthonic acids. By conducting a systematic comparison of phosphorus and arsenic systems with the evolving chemistry of antimony and the nascent exploration of bismuth analogues, we clarify fundamental constraints, expose unresolved questions, and map promising avenues for future progress in group 15 chemistry.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"9 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-11-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149305201","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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Steric hindrance enables a weakly solvating monoether electrolyte for stable lithium metal batteries 空间位阻使得一种弱溶剂化的单醚电解质能够用于稳定的锂金属电池

IF 7 1区化学

Inorganic Chemistry Frontiers Pub Date : 2026-11-02 DOI: 10.1039/d6qi02012g

Zikun Lin,Tangyu Gu,Yanjin Liu,Jiaxuan Yi,Yumei Li,Chao Chen,Lidan Xing,Weishan Li

{"title":"Steric hindrance enables a weakly solvating monoether electrolyte for stable lithium metal batteries","authors":"Zikun Lin,Tangyu Gu,Yanjin Liu,Jiaxuan Yi,Yumei Li,Chao Chen,Lidan Xing,Weishan Li","doi":"10.1039/d6qi02012g","DOIUrl":"https://doi.org/10.1039/d6qi02012g","url":null,"abstract":"Ether solvents possess superior reduction stability and exhibit good compatibility with lithium metal anodes. Nevertheless, conventional ether-based solvents establish strong coordination with Li+, so the derived solid electrolyte interphase (SEI) fails to meet the stringent requirements of interfacial stability for lithium metal anodes during long-term cycling. Herein, a novel weakly solvating ether-based electrolyte (MTBE) is developed by adopting methyl tert-butyl ether (MTBE-S) with a monoether structure as the solvent and lithium bis(fluorosulfonyl)imide (LiFSI) as the lithium salt. The intrinsic weak coordination between monoether groups and Li+, together with the steric hindrance of methyl and tert-butyl substituents, greatly weakens the interaction between ether oxygen groups and Li+. Accordingly, abundant anions participate in the construction of the Li+ solvation sheath, and a robust LiF-rich inorganic SEI is in situ formed on the lithium metal surface, which effectively restrains interfacial parasitic reactions. Furthermore, the optimized electrolyte delivers an improved Li+ transference number and accelerated interfacial charge transfer kinetics, enabling uniform Li deposition behavior. Electrochemical measurements confirm that the lithium metal anode with the MTBE electrolyte achieves a high coulombic efficiency of 98.2%. When paired with high-loading LiFePO4 cathodes and 50 μm thin Li anodes to assemble full batteries with an N/P ratio of 3.1, the MTBE electrolyte significantly enhances the cycling durability and high-temperature (45 °C) stability of full cells. This work provides an innovative strategy for the rational design and modulation of weakly solvating ether electrolytes for high-performance lithium metal batteries.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"11 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-11-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149304788","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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Correction: Surfactant-assisted synthesis of semiconductor hybrid Cd/Hg-selenidostannates with enhanced optoelectronic and piezoelectric properties 修正：表面活性剂辅助合成具有增强光电和压电性能的半导体杂化镉/氢硒酸盐

IF 7 1区化学

Inorganic Chemistry Frontiers Pub Date : 2026-11-02 DOI: 10.1039/d6qi90091g

Mohamed Saber Lassoued,Yue-Qiao Hu,Faizan Ahmad,Yan-Zhen Zheng

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π-Extended biscyclometalated Ir() and Rh() complexes as highly active and versatile visible-light photocatalysts π-扩展双环金属化Ir（）和Rh（）配合物作为高活性和多功能可见光催化剂

IF 7 1区化学

Inorganic Chemistry Frontiers Pub Date : 2026-10-30 DOI: 10.1039/d6qi01827k

Carlos Gonzalo-Navarro,Ana M. Rodríguez,Gregorio Castañeda,Juan Angel Organero,Blanca R. Manzano,Gema Durá

{"title":"π-Extended biscyclometalated Ir() and Rh() complexes as highly active and versatile visible-light photocatalysts","authors":"Carlos Gonzalo-Navarro,Ana M. Rodríguez,Gregorio Castañeda,Juan Angel Organero,Blanca R. Manzano,Gema Durá","doi":"10.1039/d6qi01827k","DOIUrl":"https://doi.org/10.1039/d6qi01827k","url":null,"abstract":"The development of new photocatalysts capable of promoting visible-light-driven organic transformations at very low catalyst loadings remains a key challenge in photoredox catalysis. Herein, we report the synthesis, characterization, and photophysical properties of a new organometallic Rh(iii) complex bearing a π-extended C^N ligand [Rh(pbpn)2(bpy)]PF6 (pbpn, 4,9,16-triazadibenzo[a,c]naphthacene), together with a comparison of its electrochemical and photocatalytic properties with those of two Ir(iii) analogues featuring ligands with different degrees of π-extension. Although the Ir(iii) congeners have been previously synthesized, their application in photocatalysis has not been investigated. TD-DFT studies explain the complexes’ behaviour and indicate that the pbpn ligand stabilizes low-lying ligand-centered triplet states, which may contribute to the improved photocatalytic performance. The excited-state redox potentials reveal the strong oxidizing and reducing capabilities of all three derivatives. The complexes were evaluated in synthetically relevant visible-light-mediated transformations, including reactions of N-heterocyclic substrates and C–S bond formation. Notably, the thiocyanation of phenylacetylene using cyclometalated Ir(iii) and Rh(iii) photocatalysts is described for the first time. In general, significantly lower PC-to-substrate ratios than those previously reported were sufficient to achieve excellent conversions with high selectivity. Remarkably, the best photocatalyst reported in this work based on Ir(iii) with the pbpn ligand achieved up to 99% yield in the reactions evaluated using PC loadings as low as 0.01–0.05 mol%. Overall, this study establishes comparative structure–property–activity relationships for a family of Ir(iii) and Rh(iii) photocatalysts and demonstrates how π-extended ligand architectures can be used to achieve remarkable results in the photocatalytic behavior of underexplored Rh(iii) platforms.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"1 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149303287","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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Electronic configurations of low-valent bis(cyclopentadienyl) metallocenes 低价双（环戊二烯基）茂金属的电子构型

IF 7 1区化学

Inorganic Chemistry Frontiers Pub Date : 2026-10-30 DOI: 10.1039/d6qi02271e

Anand Chekkottu Parambil,Akseli Mansikkamäki

{"title":"Electronic configurations of low-valent bis(cyclopentadienyl) metallocenes","authors":"Anand Chekkottu Parambil,Akseli Mansikkamäki","doi":"10.1039/d6qi02271e","DOIUrl":"https://doi.org/10.1039/d6qi02271e","url":null,"abstract":"The ground-state electronic configurations of actinide bis(cyclopentadienyl) metallocenes, metallocene anions and metallocenium cations [AnCpiPr52]m (CpiPr5 = pentaisopropylcyclopentadienyl, An = Ac–Lr, m = −2, −1, 0, +1) were determined by scalar-relativistic density functional theory calculations. The calculations included all actinides in the low oxidation states from 0 to +3. The results show that the actinide elements Pu, Am, Bk, Cf, Es, Fm, Md and No have a clear pattern in their electronic configurations in the various oxidation states and involve the occupation of the 5f shell and, in the oxidation states +1 and 0, also a toroidal orbital that is a mixture of the 7s and 6dz2 orbitals. The remaining actinide elements Ac, Th, Pa, U, Np, Cm and Lr have less clear patterns in their electronic configurations and, in some of their low oxidation states, involve the occupation of 6d orbitals that are δ-symmetric with respect to the metal–ligand bonds. The electronic configurations in the metallocene complexes are analogous to trends in the configurations of free actinide atoms and ions, and allow the actinides to be divided into two distinct categories based on their electronic configurations. The results show that there is a “break” in the actinide series between Np and Pu as predicted earlier in the literature. However, the transition after the “break” is not complete and Cm and Lr remain exceptions with electronic configurations more similar to those before the “break”. Study of calculated redox potentials and orbital occupations shows that the +3 oxidation state becomes increasingly unstable with respect to reduction to the +2 oxidation state in the heavier actinides. In the case of Fm, Md and No the +3 oxidation state is not available in bis(cyclopentadienyl) complexes as the trivalent actinide ion oxidizes the cyclopentadienyl ligands. The +1 oxidation state is the lowest limit, and the zerovalent oxidation state is outside the reach of redox chemistry.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"15 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149303286","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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Reductive Coupling of Ketones and Nitriles at a Geometrically Constrained Silanide 几何约束硅烷中酮和腈的还原偶联

IF 7 1区化学

Inorganic Chemistry Frontiers Pub Date : 2026-10-29 DOI: 10.1039/d6qi01961g

Pamela Adienes Benzan Lantigua,María Sansores-Paredes,Martin Lutz,Marc-Etienne Moret

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A 2-D hexaruthenium molecular nanocluster displaying mixed localized/delocalized metal-metal bonds 二维六砷分子纳米团簇显示混合的定域/离域金属-金属键

IF 7 1区化学

Inorganic Chemistry Frontiers Pub Date : 2026-10-28 DOI: 10.1039/d6qi02240e

Cristiana Cesari,Marco Bortoluzzi,Giulio Bresciani,Cristina Femoni,Tiziana Funaioli,Maria Carmela Iapalucci,Stefano Zacchini

{"title":"A 2-D hexaruthenium molecular nanocluster displaying mixed localized/delocalized metal-metal bonds","authors":"Cristiana Cesari,Marco Bortoluzzi,Giulio Bresciani,Cristina Femoni,Tiziana Funaioli,Maria Carmela Iapalucci,Stefano Zacchini","doi":"10.1039/d6qi02240e","DOIUrl":"https://doi.org/10.1039/d6qi02240e","url":null,"abstract":"Despite their fundamental relevance for the comprehension of chemical bonding and reactivity, 2-D molecular metal nanoclusters are still very rare and understudied. Herein, we report a straightforward and high yield synthesis of the planar hexaruthenium nanocluster [NEt4]2[Ru6S3(CO)15] (2), which has been obtained from the reaction of [NEt4][HRu3(CO)11] (1) with a slight excess of S8 in DMF or DMSO at 150 °C for 4 hours. The molecular structure of 2 has been determined by a Ru6 triangular raft-like structure. The three external Ru3 triangles of this perfectly planar hexaruthenium nanocluster are capped on the same side by three µ3-sulfido ligands. The resulting structure is reminiscent of sulfur atoms adsorbed on a compact metal surface. SC-XRD analyses show the presence of nine Ru-Ru contacts which may be considered as bonds. Computational studies point out that the six external Ru-Ru contacts are localized two centers – two electrons (2c-2e) bonds, whereas a delocalized three centers – four electrons (3c-4e) bond is present within the inner Ru3 triangle. Overall, it seems that already at this size-scale, a transition between localized and delocalized bonding is occurring on such 2-D organometallic nanoclusters.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"5 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149271964","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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Oxymethylene Intermediates in the Zeolite-Catalyzed Methanol-to-Hydrocarbons Reaction 沸石催化甲醇制烃反应中的甲氧甲烷中间体

IF 7 1区化学

Inorganic Chemistry Frontiers Pub Date : 2026-10-28 DOI: 10.1039/d6qi01624c

Mingyu Yi,Shican Jiang,Yunfan Wang,Qingfeng Zhang,Abhishek Dutta Chowdhury

{"title":"Oxymethylene Intermediates in the Zeolite-Catalyzed Methanol-to-Hydrocarbons Reaction","authors":"Mingyu Yi,Shican Jiang,Yunfan Wang,Qingfeng Zhang,Abhishek Dutta Chowdhury","doi":"10.1039/d6qi01624c","DOIUrl":"https://doi.org/10.1039/d6qi01624c","url":null,"abstract":"Dimethoxymethane (DMM) is a formaldehyde-derived oxygenate that can participate in the evolving reaction network of zeolite-catalyzed methanol-to-hydrocarbons (MTH) conversion. Although formaldehyde-derived chemistry has been linked to aromatic hydrocarbon pool (HCP) growth, hydrogen transfer reactions, and catalyst deactivation, the role of zeolite topology in governing this response remains insufficiently understood. Here, standalone DMM conversion was employed as a “probe reaction” to examine topology-dependent hydrocarbon production over a series of zeolites spanning small-, medium-, and large-pore frameworks. The catalytic response under DMM feed was systematically benchmarked against conventional MTH conversion. DMM induced a framework-dependent redistribution of hydrocarbon products rather than a universal shift toward aromatics. Cage-based small-pore zeolites and mordenite preferentially formed short olefins, whereas connected medium-pore frameworks and large-pore Beta zeolite exhibited strong aromatic enrichment. A hydrogen-balance analysis of the product distributions shows that DMM replaces paraffin-forming hydrogen-transfer aromatization by formaldehyde-mediated routes, whereas the topology decides whether the resulting hydrogen-deficient carbon leaves the catalyst as aromatics or is retained inside it. These results establish zeolite topology as a key descriptor governing the catalytic response to DMM-derived chemistry and provide a framework-level protocol for controlling olefin-aromatic selectivity under oxygenate-rich MTH conditions.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"2017 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149271967","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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Carbide-Anchored Pentanuclear Nickel Clusters as Flexible Platforms for Small-Molecule Activation and Catalysis 碳化物锚定五核镍簇作为小分子活化和催化的柔性平台

IF 7 1区化学

Inorganic Chemistry Frontiers Pub Date : 2026-10-28 DOI: 10.1039/d6qi02103d

Manar M. Shoshani,Junyang Liu,Kethya Sum,Samuel A. Johnson

{"title":"Carbide-Anchored Pentanuclear Nickel Clusters as Flexible Platforms for Small-Molecule Activation and Catalysis","authors":"Manar M. Shoshani,Junyang Liu,Kethya Sum,Samuel A. Johnson","doi":"10.1039/d6qi02103d","DOIUrl":"https://doi.org/10.1039/d6qi02103d","url":null,"abstract":"The reactivity of a pentanuclear carbide cluster, [(iPr3P)Ni]5(µ5-C)H4 (1), with a variety of reagents was examined. The addition of 3,5-bis(trifluoromethyl)aniline to 1 resulted in reversible N-H bond oxidative addition, forming [(iPr3P)NiH]5(µ4-C)[N(H)C6H3(m-CF3)2] (2), with a [Ni5]10+ core. Exposing 1 to neopentyl chloride produced the paramagnetic nickel carbide cluster [(iPr3P)Ni]5(µ5-C)H4(µ2-Cl) (3) from a one-electron oxidation, as well as the homodimerized product 2,2,5,5-tetramethylhexane. The reaction of 1 with iPr3P=S occurred with a net transfer of the sulfur to give [(iPr3P)Ni]5(µ5-C)H4(S) (4). When 1 was exposed to ammonia-borane, BH3 was incorporated to form [(iPr3P)Ni]5(µ6-C)H4(BH3) (5) with a short B-C interaction. Carbide complex 1 reacts reversibly with H2 to give tentatively assigned [(iPr3P)Ni]5(µ5-C)H6 (6). Complex 1 catalyzes the hydrosilylation of neohexene by Ph2SiH2 via an intermediate tentatively assigned as the adduct [(iPr3P)Ni]5(µ5C)H4(H2SiPh2) (7). All results demonstrate that despite variable coordination numbers, the carbide ligand can act as an anchoring ancillary ligand that supports geometrically flexible and atypically reactive pentanuclear clusters, even in cases like 5, where the carbide forms bonding interactions with the incoming BH3.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"4 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149271965","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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Stannylene Hydride-Mediated Hydrodefluorination in Redox-Neutral Sn(II) Catalysis 氧化还原中性锡（II）催化中锡氢化物介导的加氢除氟反应

IF 7 1区化学

Inorganic Chemistry Frontiers Pub Date : 2026-10-28 DOI: 10.1039/d6qi02146h

Iris Ballmaier,Destiny L. T. Brumm,Tobias Morack

{"title":"Stannylene Hydride-Mediated Hydrodefluorination in Redox-Neutral Sn(II) Catalysis","authors":"Iris Ballmaier,Destiny L. T. Brumm,Tobias Morack","doi":"10.1039/d6qi02146h","DOIUrl":"https://doi.org/10.1039/d6qi02146h","url":null,"abstract":"Low-valent tin hydrides display hydride donor properties that differ markedly from those of conventional organotin(IV) hydrides, yet their catalytic applications have remained largely confined to reactions of polar multiple bonds. Herein, we exploit this distinct reactivity for catalytic C-F bond activation and investigate the mechanism underlying the hydrodefluorination of polyfluoroarenes. An isolable diketiminate-supported Sn(II) fluoride efficiently catalyses the reaction using phenylsilane as terminal hydride source. Stoichiometric and spectroscopic studies establish rapid fluoride-hydride exchange between the stannylene fluoride and phenylsilane, generating a catalytically competent stannylene hydride that directly reacts with polyfluoroarenes to form the hydrodefluorination product and regenerate the Sn(II) fluoride. Density functional theory calculations of its hydricity reveals a substantially greater thermodynamic propensity for hydride transfer than nBu3SnH and further distinguish between two plausible pathways for C-F activation: direct hydride transfer proceeds through concerted nucleophilic aromatic substitution (cSNAr) and is favoured over competing oxidative addition to Sn(II). The resulting catalytic cycle therefore operates entirely at Sn(II), combining fluoride-hydride exchange with polar C-F substitution rather than Sn(II)/Sn(IV) redox cycling. These findings establish lowvalent tin hydrides as competent intermediates for catalytic C-F bond activation and illustrate how their pronounced hydride donor ability can extend the mechanistic toolbox of stannylene catalysis.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"22 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149271973","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