Dalton Transactions最新文献_第3页

Switching of magnetic and polarization characteristics in response to intramolecular ligand-metal electron transfer in dinuclear [FeCo] compounds. 双核[FeCo]化合物中响应分子内配金属电子转移的磁性和极化特性的切换。

IF 3.3 3区化学

Dalton Transactions Pub Date : 2026-10-20 DOI: 10.1039/d6dt01478j

Serghei Ostrovsky, Sophia Klokishner

{"title":"Switching of magnetic and polarization characteristics in response to intramolecular ligand-metal electron transfer in dinuclear [FeCo] compounds.","authors":"Serghei Ostrovsky, Sophia Klokishner","doi":"10.1039/d6dt01478j","DOIUrl":"10.1039/d6dt01478j","url":null,"abstract":"A theoretical model has been developed to describe the spin transformation in the [(Fe(RR-cth))(Co(SS-cth))(μ-dhbq)](AsF6)3 compound, accompanied by a change in macroscopic polarization caused by electron density redistribution due to reversible intramolecular electron transfer between the μ-dhbq ligand and Fe ion. In this model, the states of a single complex arising from its three configurations are accounted: low-spin-Fe3+-dhbq3--low-spin-Co3+, high-spin-Fe3+-dhbq3--low-spin-Co3+ and high-spin-Fe2+-dhbq2--low-spin-Co3+. Due to the molecular structure of the compound demonstrating this transformation, the interaction between the molecular modes forming the spectrum of a single complex and the crystalline modes assuring cooperativity in the system is assumed to be responsible for the spin transformation. This model also includes the dipole-dipole interaction between complexes in the whole crystal responsible for electron density redistribution caused by electron transfer. The problem of interacting complexes is solved in the mean field approximation. On the basis of the developed model, a comprehensive explanation of the magnetic and polarization characteristics of the [(Fe(RR-cth))(Co(SS-cth))(μ-dhbq)](AsF6)3 compound is given. The inclusion of the intermediate excited configuration high-spin Fe3+-dhbq3--low-spin-Co3+, along with the ground and final configurations of the FeCo dimeric complex in the model, allows for the explanation of the unusual increase in the macroscopic polarization observed after the low-spin → high-spin transition in the iron ion is completed.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" ","pages":"14384-14393"},"PeriodicalIF":3.3,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149101052","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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

Archaeoglobus fulgidus CbiX^S is a promiscuous chelatase with a broad substrate scope. fulgidus Archaeoglobus chixs是一种杂交螯合酶，具有广泛的底物范围。

IF 3.3 3区化学

Dalton Transactions Pub Date : 2026-10-20 DOI: 10.1039/d6dt01532h

Bruce S Lickey, Matthew D Liptak

{"title":"Archaeoglobus fulgidus CbiXS is a promiscuous chelatase with a broad substrate scope.","authors":"Bruce S Lickey, Matthew D Liptak","doi":"10.1039/d6dt01532h","DOIUrl":"10.1039/d6dt01532h","url":null,"abstract":"Organisms biosynthesize square planar metal tetrapyrrole cofactors containing Mg, Fe, Co, and Ni using chelatase enzymes, which selectively insert the correct metal into a specific organic ligand. Archaeoglobus fulgidus CbiXS has been proposed to be an \"ancestral\" chelatase enzyme; in this work we have evaluated its substrate scope to ascertain whether this enzyme is a promising starting point for synthetic chelatase design. Size-exclusion chromatography revealed that CbiXS is a tetramer in solution regardless of the metalation state of the enzyme, in contrast to the dimeric structure of the nickel chelatase CfbA. Reaction conditions that minimize enzyme-free metal insertion into tetrapyrroles were determined, which revealed that many of the in vitro activity assays reported in the literature for chelatase enzymes may be plagued by non-enzymatic metal insertion. Under these conditions that minimize uncatalyzed metal insertion, CbiXS was observed to catalyze metal insertion for six different combinations of metal and tetrapyrrole. Based upon the turnover numbers of these reactions, CbiXS is most effective at catalyzing metal insertion for reactants similar to its native substrates: cobalt and sirohydrochlorin. Kinetic analysis for reactions with varying substrate concentrations revealed that CbiXS may be substrate-inhibited for non-native substrates. In addition, the kinetic data identifies metal-ligand bond formation as the rate-limiting step of the enzyme. Due to its broad substrate scope, CbiXS is an encouraging starting point for synthetic chelatase design that could yield non-natural metal tetrapyrroles for use in the biotechnology sector.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" ","pages":"14614-14624"},"PeriodicalIF":3.3,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149101105","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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

Mechanism of the dehydrogenation of Mg(BH₄)₂·THF_0.25 to Mg(B₁₀H₁₀): role of the THF solvate. Mg(BH4)2·THF0.25脱氢生成Mg（B10H10）的机理：THF溶剂的作用

IF 3.3 3区化学

Dalton Transactions Pub Date : 2026-10-20 DOI: 10.1039/d6dt02098d

McKinley A Prager, Sunil Shrestha, Phuong Q H Nyugen, Natalie McNurlin, Stephen Kim, Craig M Jensen

{"title":"Mechanism of the dehydrogenation of Mg(BH4)2·THF0.25 to Mg(B10H10): role of the THF solvate.","authors":"McKinley A Prager, Sunil Shrestha, Phuong Q H Nyugen, Natalie McNurlin, Stephen Kim, Craig M Jensen","doi":"10.1039/d6dt02098d","DOIUrl":"10.1039/d6dt02098d","url":null,"abstract":"Dehydrogenation of Mg(BH4)2·THFx (1·THF) at 180 °C has been previously found to produce primarily a mixture of Mg(B3H8)2 (2) and Mg(B10H10) (3). It has now been found that dehydrogenation under a H2 back pressure of 20 bar suppresses the formation of 2 and results in very high (>95%) selectivity for 3. The production of 3 is not inhibited by hydrogen pressure. This demonstrates that the reaction pathway leading to its formation does not involve reversible, rate limiting H2 elimination and is divergent from the pathway leading to 2. Unlike the pathway leading to the formation of 2, the dehydrogenation of 1·THF to 3 is irreversible under moderate conditions. Concurrent with the dehydrogenation reaction, THF is slowly converted to Mg(OBun)2, curtailing the production 3. However, the dehydrogenation process is revived by addition of a fresh aloquate of THF to the reaction mixtures. It is hypothesized that THF enables the production of 3 by stabilizing the key intermediate, [B2H5]- and by the low melting point (<100 °C) of 1·THF which allows long-range diffusion of borane anions at much lower energies than those required for their transport in the solid-state.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" ","pages":"14521-14525"},"PeriodicalIF":3.3,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149101060","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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

A biphenyl-bridged bis(cyclen) cyclophane: Ag(I)-induced conformational reorganization and successive Ag(I) binding. 联苯桥接双（环）环烷：Ag(I)诱导的构象重组和连续的Ag(I)结合。

IF 3.3 3区化学

Dalton Transactions Pub Date : 2026-10-20 DOI: 10.1039/d6dt02170k

Hiroki Horita, Eunji Lee, Mari Ikeda, Shunsuke Kuwahara, Yoichi Habata

引用次数: 0

A tris(3,5-dimethylpyrazolyl)borate-supported germanium(IV) Lewis acid. 三（3,5-二甲基吡唑）硼酸负载的锗（IV）路易斯酸。

IF 3.3 3区化学

Dalton Transactions Pub Date : 2026-10-20 DOI: 10.1039/d6dt01955b

Jerin Joseph, Archana P V, Alex P Andrews, Ganping Wang, Laurent Maron, Ajay Venugopal

引用次数: 0

Concentration-driven faceting of MgO polyhedra boosts glucose isomerization in water. 浓度驱动的氧化镁多面体面化促进了葡萄糖在水中的异构化。

IF 3.3 3区化学

Dalton Transactions Pub Date : 2026-10-20 DOI: 10.1039/d6dt02360f

Kaiyue Cheng, Lin Gan, Meiqi Zheng, Wenying Shi, Xianggui Kong, Mingfei Shao

引用次数: 0

Topochemical synthesis of ternary metal sulfides including new LaAgS₂. 含新LaAgS2的三元金属硫化物的拓扑化学合成。

IF 3.3 3区化学

Dalton Transactions Pub Date : 2026-10-20 DOI: 10.1039/d6dt02059c

Glen R Hebberd, Toby J Blundell, Leon Bowen, Stewart J Clark, Emma E McCabe

引用次数: 0

Ionic-Liquid-Regulated Interfacial Coordination Reconstruction of Uranyl(VI) Species during Tributyl Phosphate Extraction

IF 4 3区化学

Dalton Transactions Pub Date : 2026-10-20 DOI: 10.1039/d6dt01773h

Zongtai Wang,Jie Jiang,Xin Wang,Xuesong Peng,Linghui Meng,Yaqiang Li,Ruopeng Li,Liudong Hou,Maozhong An,Jing Ma

{"title":"Ionic-Liquid-Regulated Interfacial Coordination Reconstruction of Uranyl(VI) Species during Tributyl Phosphate Extraction","authors":"Zongtai Wang,Jie Jiang,Xin Wang,Xuesong Peng,Linghui Meng,Yaqiang Li,Ruopeng Li,Liudong Hou,Maozhong An,Jing Ma","doi":"10.1039/d6dt01773h","DOIUrl":"https://doi.org/10.1039/d6dt01773h","url":null,"abstract":"The extraction and separation of uranyl species from nitric acid media are critical processes in nuclear fuel reprocessing, while the molecular-level coordination mechanism remains insufficiently understood. Herein, the extraction behavior and mechanism of U(VI) in the tributyl phosphate (TBP)/tributylmethylphosphonium bis(trifluoromethanesulfonyl)imide ([P1444][NTf2]) ionic liquid system were systematically investigated by combining experiments with molecular simulations. The results demonstrate efficient U(VI) extraction, rapid kinetics, and good temperature adaptability. Slope analysis and ion competition experiments reveal that extraction involves TBP-assisted coordination coupled with cation-exchange contributions, indicating dynamic solvation and coordination reconstruction during phase transfer. Electrostatic potential and dipole moment analyses indicate that the ionic-liquid environment modifies the electronic distribution of TBP and increases its polarization, particularly around the phosphoryl (P=O) group, potentially influencing its interactions with uranyl species. Molecular dynamics simulations reveal a sequential extraction process involving interfacial enrichment, coordination reconstruction, and phase transfer. At the aqueous–organic interface, U(VI)-containing species undergo partial dehydration and accumulate at the interface. TBP progressively enters the first coordination sphere of U(VI), replacing some coordinated water molecules, while some nitrate ligands remain in the first coordination sphere. Upon transfer into the ionic liquid phase, TBP becomes the dominant coordinating ligand and stabilizes TBP-rich uranium complexes. Overall, this work demonstrates that U(VI) extraction in the TBP/[P1444][NTf2] system is governed by an ionic-liquid-regulated interfacial coordination reconstruction process, where electronic modulation and dynamic ligand exchange collectively promote efficient uranium transfer.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"34 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149225809","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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

Acid medium effects on scandium extraction and coordination chemistry with an amine-triamide extractant for red mud processing

IF 4 3区化学

Dalton Transactions Pub Date : 2026-10-20 DOI: 10.1039/d6dt02047j

Xueyu Wang,Shimeng Li,Qiao Yu,Yiting Wang,Yan Zhao,Songdong Ding

{"title":"Acid medium effects on scandium extraction and coordination chemistry with an amine-triamide extractant for red mud processing","authors":"Xueyu Wang,Shimeng Li,Qiao Yu,Yiting Wang,Yan Zhao,Songdong Ding","doi":"10.1039/d6dt02047j","DOIUrl":"https://doi.org/10.1039/d6dt02047j","url":null,"abstract":"The recovery of scandium from red mud meets two intertwined challenges: the overwhelming abundance of coexisting impurities, which renders conventional extractants poorly selective, and the lack of a systematic understanding of how the acid medium modulates extractant coordination chemistry and, consequently, separation efficiency. To address this, we comprehensively investigated the extraction and coordination of Sc3+ with the tripodal amine-triamide extractant NTAamide(n Oct) (denoted as L) in HNO3, HCl, and H2SO4 media. Slope analysis and spectroscopic titration consistently confirm the formation of stable 1:2 Sc:L complexes in all three systems. Mechanistic studies further reveal that the ligand affinity toward Sc3+ decreases in the order NO3– > Cl⁻ > SO42⁻, which originates from the varying strength of Sc3+-anion interactions, and together with differences in anion hydration energies, leads to the extraction efficiency sequence of HNO3 > HCl > H2SO4. Notably, in the most favorable HNO3 system, the separation factors of Sc3+ over common impurities (Na+, Mg2+, Al3+, Ca2+, Ti4+, Mn2+, Fe3+, and Y3+) reach 102–104 at 0.01 mol/L HNO3 and remain remarkably high even at 5.0 mol/L, substantially outperforming conventional extractants. To fill this critical knowledge gap, we establish, for the first time, a direct correlation between the acid medium, the coordination chemistry of N,O-donor extractants, and the resulting extraction performance, thereby providing a rational and predictive framework for selecting optimal acid media for this class of extractants in red mud processing.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"1 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149225840","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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

Field-induced single-molecule magnetism in aminyl radical bridged trinuclear lanthanide clusters 氨基基桥接三核镧系元素团簇的场致单分子磁性

IF 4 3区化学

Dalton Transactions Pub Date : 2026-10-19 DOI: 10.1039/d6dt01945e

Dan Liu,Changjiang Wu,Qiang Liu,Huayi Fang,Yin-Shan Meng

引用次数: 0