Chemistry - A European Journal最新文献_第8页

Metalized Borylene in Boron-Gold Carbonyl Complexes: Infrared Spectra and Theoretical Calculations. 硼金羰基复合物中的金属化硼烯：红外光谱和理论计算。

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2024-11-19 DOI: 10.1002/chem.202403368

Xuefeng Wang, Jin Hu

{"title":"Metalized Borylene in Boron-Gold Carbonyl Complexes: Infrared Spectra and Theoretical Calculations.","authors":"Xuefeng Wang, Jin Hu","doi":"10.1002/chem.202403368","DOIUrl":"https://doi.org/10.1002/chem.202403368","url":null,"abstract":"Borylenes (:B-R), built on a single B-R bond between boron and another nonmetallic atom or group, are a heated subject of special interest due to their intriguing transition-metal-mimicking reactivity, but the relative lack of understanding for the electronic structure and chemical bonding of transition metal borides leads to lingering neglect of metalized borylenes (:B-M) based on covalent B-M bonding. Here we use infrared photodissociation spectroscopy in combination with density functional calculations to study the geometric structure and chemical bonding of boron-gold carbonyl complex cations. The structure and bonding analyses demonstrated that the BAu(CO)3+ and BAu2(CO)4+ complexes can be described as bis-carbonyl-trapped borylene adducts. While the metal-rich BAu3(CO)4+ complex represents an unusual multicenter-bond-stabilized borylene cation with excellent σ-acidity and π-backbonding capability for CO activation, featuring Cs symmetry with a quasi-T-shaped BAu3+ core. It is manifested that BAu3+ presents greater amphoteric reactivity and improved stability compared to BAu1,2+ due to the presence of the three-center-two-electron Au-B-Au bond. This study discloses a conceptually new platform for accessing reactive metalized borylenes by exploiting the boron-mediated multicenter-bond stabilization strategy and using more bench-stable and ubiquitous metal carbonyl fragments as starting materials, thus providing a broader opportunity for the design of novel chemical structures and catalysts.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202403368"},"PeriodicalIF":3.9,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142674642","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Magnetohydrodynamic Enhancement of Biofuel Cell Performance. 增强生物燃料电池性能的磁流体动力学。

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2024-11-19 DOI: 10.1002/chem.202403329

Gerardo Salinas, Tatjana Safarik, Marta Meneghello, Sabrina Bichon, Sebastien Gounel, Nicolas Mano, Alexander Kuhn

{"title":"Magnetohydrodynamic Enhancement of Biofuel Cell Performance.","authors":"Gerardo Salinas, Tatjana Safarik, Marta Meneghello, Sabrina Bichon, Sebastien Gounel, Nicolas Mano, Alexander Kuhn","doi":"10.1002/chem.202403329","DOIUrl":"10.1002/chem.202403329","url":null,"abstract":"Biofuel cells have become an interesting alternative for the design of sustainable energy conversion systems with multiple applications ranging from biosensing and bioelectronics to autonomously moving devices. However, as an electrochemical system, their performance is intimately related to mass transport conditions. In this work, the magnetohydrodynamic (MHD) effect is studied as an easy and straightforward alternative to enhance the performance of a biofuel cell based on the enzymes glucose oxidase (GOx) and bilirubin oxidase (BOD). The synergetic effect between the electric and ionic currents, produced by the enzymatic redox reactions, and a magnetic field orthogonal to the surface of the electrodes, leads to the formation of localized magnetohydrodynamic vortexes. Such an integrated convective regime generates an increase of the bioelectrocatalytic current and its concomitant power output in the presence of the external magnetic field. In addition, by fine-tuning the spatial arrangement of the anode and cathode, it is possible to benefit from the sum of anodic and cathodic MHD vortexes, leading to an enhanced power output of up to 300%.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202403329"},"PeriodicalIF":3.9,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142666527","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Terphenyl-Ge as µ2-Ge-bis(hexahapto-Trip) Bridging Ligand to Form a New Transition Metal-Only Chelating Lewis Base. 三联苯-锗作为 µ2-Ge 双（六巯基-三）桥接配体，形成一种新的过渡金属螯合路易斯碱。

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2024-11-19 DOI: 10.1002/chem.202404201

Johanna Manegold, Adrian Ebisch, Klaus Eichele, Hartmut Schubert, Lars Wesemann

{"title":"Terphenyl-Ge as µ2-Ge-bis(hexahapto-Trip) Bridging Ligand to Form a New Transition Metal-Only Chelating Lewis Base.","authors":"Johanna Manegold, Adrian Ebisch, Klaus Eichele, Hartmut Schubert, Lars Wesemann","doi":"10.1002/chem.202404201","DOIUrl":"https://doi.org/10.1002/chem.202404201","url":null,"abstract":"Terphenylgermanium Ar*Ge [Ar* = C6H3(2,6-Trip)2, Trip = 2,4,6-C6H2iPr3] was found to act as a novel µ2-Ge-bis(hexahapto-Trip) bridging ligand. Deprotonated terphenyl germanium trihydride [Li(thf)3][Ar*GeH2] (1) undergoes reductive elimination and transfer of hydrogen in reaction with dimeric [(COD)RhCl]2 to yield the dinuclear complex [Ar*GeRh(COE)RhCl(COD)] (2). Subsequent chloride abstraction from compound 2 using Na[BArF4] or Li[Al(OtBuF)4] results in the cationic complexes [Ar*GeRh(COE)Rh(COD)][WCA] (3) {WCA : [BArF4]- (ArF = C6H3-3,5-(CF3)2), [Al(OtBuF)4]-}. Ligand exchange of olefin for CO yields the carbonyl complex [Ar*Ge(Rh(CO))2][BArF4] (4). In an alternative approach to the synthesis of carbonyl complex 4, [Li(thf)3][Ar*GeH2] (1) was treated with [Rh(CO)2Cl]2 leading to the isolation of a hexanuclear rhodium cluster [(µ3-Ar*Ge)2{Rh(CO)2}6(µ3-H)2] (5) in reasonable yield. In reactions with [Rh(CO)2Cl]2 or [Ph3PAuCl] complex 4 abstracts the chloride ligand and forms tetranuclear complexes featuring a GeRh3- or GeRh2Au-rectangle, [Ar*GeCl(Rh3(CO)4)][BArF4] (6), or [Ar*GeCl{Rh2(CO)2}(AuPPh3)][BArF4] (7).","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202404201"},"PeriodicalIF":3.9,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142674645","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Dual-Coreactants Enhanced Electrochemiluminescence. 双核反应物增强电化学发光。

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2024-11-19 DOI: 10.1002/chem.202403804

Jialian Ding, Bin Su

引用次数: 0

A Multistep Oxidative Cascade Reaction from a Naphthalenediol-Based pre-Ligand to a Tetranuclear Perylenequinone-Based FeIII Complex. 从基于萘二醇的前配体到基于过醌的四核 FeIII 复合物的多步氧化级联反应。

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2024-11-19 DOI: 10.1002/chem.202403690

Jasmin Finke, Jan Oldengott, Anja Stammler, Thorsten Glaser

{"title":"A Multistep Oxidative Cascade Reaction from a Naphthalenediol-Based pre-Ligand to a Tetranuclear Perylenequinone-Based FeIII Complex.","authors":"Jasmin Finke, Jan Oldengott, Anja Stammler, Thorsten Glaser","doi":"10.1002/chem.202403690","DOIUrl":"10.1002/chem.202403690","url":null,"abstract":"We have developed a family of dinuclear complexes using 2,7-disubstituted 1,8-naphthalenediol ligands that bind by molecular recognition to two neighboring phosphate diesters of the DNA backbone with the dinuclear CuII and NiII complexes exhibiting a severe cytotoxicity for human cancer cells. To increase the binding affinity, we intended to synthesize the corresponding dinuclear FeIII complex. Surprisingly, we obtained a tetranuclear FeIII perylene-based complex instead of the expected dinuclear FeIII naphthalene-based complex. In order to establish a rational and reproducible synthesis, we carefully analyzed this reaction. This revealed a multistep oxidative cascade reaction including the pre-coordination of FeII ions in the N3-binding pockets, the Lewis-acid assisted MOM-deprotection of the pre-ligand by the pre-oriented FeII ions, two oxidative aromatic C-C coupling reactions, oxidation of the perylene-based backbone and of FeII to FeIII. The careful analysis of bond lengths, HOMA indices (harmonic oscillation model of aromaticity), FTIR and UV-Vis-NIR spectra supported by DFT calculations reveals the presence of an aromatic 18-electron oxidized perylenequinone ligand backbone. In summary, a multistep cascade reaction involving in total a 10-electron oxidation has been established for the straight-forward synthesis of an unprecedented perylenequinone-based ligand system.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202403690"},"PeriodicalIF":3.9,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142666525","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Metal Pyrazolyl-diphosphonate Pillared Materials as Heterogeneous Catalysts in the Mukaiyama-type Aerobic Olefin Epoxidation. 作为 Mukaiyama 型有氧烯烃环氧化作用中的异相催化剂的吡唑基二膦酸金属柱状材料。

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2024-11-19 DOI: 10.1002/chem.202403756

Nikolaos Giakoumakis, Elpiniki Chachlaki, Duane Choquesillo-Lazarte, Kostas D Demadis

引用次数: 0

The Emissive and Electrochemical Properties of Hypervalent Pyridine-Dipyrrolide Bismuth ComplexesThe Emissive and Electrochemical Properties of Hypervalent Pyridine-Dipyrrolide Bismuth Complexes. 高价吡啶-二吡咯烷铋络合物的发射和电化学性质高价吡啶-二吡咯烷铋络合物的发射和电化学性质。

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2024-11-19 DOI: 10.1002/chem.202403761

Katharina L Deuter, Felix Kather, Michael Linseis, Michael Bodensteiner, Rainer Friedrich Winter

{"title":"The Emissive and Electrochemical Properties of Hypervalent Pyridine-Dipyrrolide Bismuth ComplexesThe Emissive and Electrochemical Properties of Hypervalent Pyridine-Dipyrrolide Bismuth Complexes.","authors":"Katharina L Deuter, Felix Kather, Michael Linseis, Michael Bodensteiner, Rainer Friedrich Winter","doi":"10.1002/chem.202403761","DOIUrl":"10.1002/chem.202403761","url":null,"abstract":"We present a series of six hypervalent bismuth complexes Bi(R1PDPR2)X bearing ligands characterized by the pyridine-2,6-bis(pyrrolide) (PDP) structural motif. While bismuth holds considerable potential for facilitating efficient intersystem crossing (ISC), reports on phosphorescent molecular bismuth complexes are still scarce and mostly based on systems that exhibit inter‑ or intraligand charge transfer character of their optical excitations. Herein, the UV/vis absorptive, luminescent, and electrochemical properties of complexes Bi(R1PDPR2)X are explored, where the substituents R1 and R2, as well as the halide ligand X are varied. These compounds are characterized by an intense HOMO®LUMO transition of mixed ligand-to-metal charge transfer (LMCT) and interligand charge transfer (LL'CT) character, as shown by time-dependent density functional theory (TD-DFT) calculations. At 77 K in a 2-MeTHF matrix, these compounds exhibit red, long-lived phosphorescence with lifetimes ranging from 671 to 20 µs. Cyclic voltammetry measurements and TD-DFT calculations show that the substituents influence HOMO and LUMO energies to almost equal extent, resulting in nearly constant emission wavelengths throughout this series. Single-crystal X-ray diffraction studies of four of the six complexes exemplify the inherent Lewis acidity of the coordinated Bi3+ ion, in spite of its hypervalency.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202403761"},"PeriodicalIF":3.9,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142666532","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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 Novel Methacryloyl-Masked NIR Fluorescent Probe for Detection of Cysteine and Its Application in Bioimaging. 用于检测半胱氨酸的新型甲基丙烯酰掩蔽近红外荧光探针及其在生物成像中的应用

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2024-11-19 DOI: 10.1002/chem.202402840

Prasad M Sonawane, Neha Jain, JunHyuk Kim, Su Jeong Park, Sandip V Mulay, Satish Balasaheb Nimse, David G Churchill

引用次数: 0

A Cascade Synthesis of Furo-Pyrrolo-Pyridines via Pd(II)-Catalyzed Dual N-H/C Annulative-Cyclization. 通过 Pd(II)-Catalyzed Dual N-H/C Annulative-Cyclization 级联合成呋喃并吡咯并吡啶。

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2024-11-18 DOI: 10.1002/chem.202403470

Hirendra Nath Dhara, Supriya Manna, Bhisma K Patel

引用次数: 0

Remarkable effect of stereoisomerism on the Am(III)/Ln(III) solvent extraction. New ligands for highly efficient separation of americium. 立体异构对 Am(III)/Ln(III) 溶剂萃取的显著影响。高效分离镅的新配体。

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2024-11-18 DOI: 10.1002/chem.202403056

Valentine S Petrov, Pavel S Lemport, Mariia V Evsiunina, Petr I Matveev, Paulina Kalle, Yulia V Nelyubina, Svetlana A Aksenova, Alexei D Averin, Alexei A Yakushev, Vitaly A Roznyatovsky, Roman V Zonov, Vladimir G Petrov, Igor P Gloriozov, Yuri A Ustynyuk, Valentine G Nenajdenko

{"title":"Remarkable effect of stereoisomerism on the Am(III)/Ln(III) solvent extraction. New ligands for highly efficient separation of americium.","authors":"Valentine S Petrov, Pavel S Lemport, Mariia V Evsiunina, Petr I Matveev, Paulina Kalle, Yulia V Nelyubina, Svetlana A Aksenova, Alexei D Averin, Alexei A Yakushev, Vitaly A Roznyatovsky, Roman V Zonov, Vladimir G Petrov, Igor P Gloriozov, Yuri A Ustynyuk, Valentine G Nenajdenko","doi":"10.1002/chem.202403056","DOIUrl":"https://doi.org/10.1002/chem.202403056","url":null,"abstract":"Two novel 1,10-phenanthroline-2,9-diamide ligands were constructed based on 2-phenylpyrrolidine and obtained as pure diastereomers. These ligands demonstrated advanced properties in liquid-liquid extraction tests. They revealed high efficiency of americium(III) extraction alongside with the record values of selectivity in the separation of americium from light lanthanides from strongly acidic media. An abrupt increase of extraction efficiency when moving along the lanthanide series from lanthanum to lutetium was observed. The examination of the extraction behavior of pure diastereomeric forms revealed noticeable differences in their selectivity while maintaining the overall extraction trend. The explanation of the discovered patterns was elucidated by a comprehensive study of the ability of the ligands to bind lanthanide nitrates in solutions. All the data collected (UV-vis and NMR titration, X-ray analysis of resulting complexes, solvation numbers estimation) were supported by quantum chemical calculation. These data clearly indicated that in case of light lanthanides the formation of 1:1 complexes is most preferable. In the same time, complexes with heavy lanthanides, such as ytterbium and lutetium, exist as ionic pairs which may consist of [L2M]z+ cations counterbalanced by metallates anions, which may result in formation of unusual composition species L2M2 or even L4M5 clusters.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202403056"},"PeriodicalIF":3.9,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142646138","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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