Dalton Transactions最新文献_第7页

A Tridentate and Dianionic N-Heterocyclic Olefin (NHO) with Two Unsymmetrically-Tethered Aryloxide Sidearms on Bismuth: A Fortuitous Followed by Systematic Discovery.

IF 4 3区化学

Dalton Transactions Pub Date : 2025-03-25 DOI: 10.1039/d5dt00706b

Santu Goswami, Subham Sarkar, Anisha Guha Roy, Dibyendu Mallick, Debabrata Mukherjee

{"title":"A Tridentate and Dianionic N-Heterocyclic Olefin (NHO) with Two Unsymmetrically-Tethered Aryloxide Sidearms on Bismuth: A Fortuitous Followed by Systematic Discovery.","authors":"Santu Goswami, Subham Sarkar, Anisha Guha Roy, Dibyendu Mallick, Debabrata Mukherjee","doi":"10.1039/d5dt00706b","DOIUrl":"https://doi.org/10.1039/d5dt00706b","url":null,"abstract":"We report here our priorly nurtured bifunctional imidaozlium-phenol LH2Br ([HO-4,6-tBu2-C6H2-2-CH2{CH(NCH=CHNAr)}]Br; Ar = Dipp = 2,6-iPr2-C6H3) leading to three distinct outcomes with bismuth by simply altering the relative ratios of the reacting components. Treating LH2Br and Bi(HMDS)3 (HMDS = N(SiMe3)2) in a 1:1 ratio gives the NHC-Bi complex [(L)BiBr(HMDS)] (1). Whereas, LH2Br, Bi(HMDS)3, and KHMDS in a 2:1:1 ratio serendipitously result to an unprecedented NHO-Bi complex [(DippNHO2ArO)BiBr] (2; Scheme 1), featuring a novel dianoinic and tridentate NHO ligand with two unsymmetric aryloxide sidearms. A tri-acidic imidazolium salt L’H3I ([HO-4,6-tBu2-C6H2-2-CH2{C(HO-4,6-tBu2-C6H2-2-CH2)(NCH=CHNMe)}]I) is synthesized independently as a potential precursor to such a NHO framework and the corresponding NHO-BiI complex [(MeNHO2ArO)Bi(-I)]2 (32) is made as the proof of concept. Lastly, treating LH2Br and Bi(HMDS)3 in a 2:1 ratio also unexpectedly leads to an ‘abnormal’ NHC-Bi complex [(aL)BiBr2(DippImd)] (4; DippImd = Dipp-imidazole). The multi-component and essentially multi-step reactions leading to 2 and 4 look challenging to fully elucidate mechanistically. Still, control experiments indicate 1 as a possible intermediate in both cases. Based on that and the prior insights on LH2Br and an intermediate LH, plausible routes for both 2 and 4 are hypothesized. DFT calculations are also carried out to analyze the bonding in 2 and 32 and to justify a NHC to aNHC isomerization towards the formation of 4.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"29 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695540","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

Salen-type nickel(II) complexes in distinct selective hydrosilylation of alkenes under mild conditions

IF 4 3区化学

Dalton Transactions Pub Date : 2025-03-25 DOI: 10.1039/d4dt03257h

Bartłomiej Szarłan, Jakub Robaszkiewicz, Piotr Pawluc, Maciej Kubicki, Maciej Zaranek

引用次数: 0

Gadolinium-doped carbon nanoparticles: coordination, spectroscopic characterization and magnetic resonance relaxivity

IF 4 3区化学

Dalton Transactions Pub Date : 2025-03-25 DOI: 10.1039/d5dt00362h

Nikita Mitiushev, Daria U. Musaeva, Daniil A. Artemov, Alexander V. Syuy, Olga S. Pavlova, Yury A. Pirogov, EN Kabachkov, Alexander Fionov, V G Kytin, Elizaveta Konstantinova, Viktor Yurevich Timoshenko, Andrey N Baranov

{"title":"Gadolinium-doped carbon nanoparticles: coordination, spectroscopic characterization and magnetic resonance relaxivity","authors":"Nikita Mitiushev, Daria U. Musaeva, Daniil A. Artemov, Alexander V. Syuy, Olga S. Pavlova, Yury A. Pirogov, EN Kabachkov, Alexander Fionov, V G Kytin, Elizaveta Konstantinova, Viktor Yurevich Timoshenko, Andrey N Baranov","doi":"10.1039/d5dt00362h","DOIUrl":"https://doi.org/10.1039/d5dt00362h","url":null,"abstract":"Carbon nanoparticles (CNPs) are attracting great attention as potential multifunctional agents for biomedical applications because of their bright fluorescence, low toxicity and flexibility of the physico-chemical properties. In the present paper, aqueous solutions of CNPs doped with gadolinium (Gd) (Gd-CNPs) in a wide range of Gd-concentration were prepared by hydrothermal synthesis. The role of Gd doping on the optical properties and magnetic resonance (MR) relaxivity of Gd-CNPs was revealed. The Gd content was determined using X-ray fluorescence and spectrophotometry analysis. The composition of surface functional groups and coordination of Gd-ions in Gd-CNPs were established by means of the IR absorption spectroscopy and X-ray photoemission spectroscopy (XPS). The optical properties of Gd-CNPs in aqueous solutions were characterized by means of the UV-visible-near-IR absorption spectroscopy and photoluminescence measurements with different excitation wavelength. The local surroundings of Gd-ions and paramagnetic centers in Gd-CNPs were probed by using the electron paramagnetic resonance (EPR) spectroscopy. The MR proton relaxation measurements in aqueous solutions Gd-CNPs were carried out to determine the role of Gd-concentration for their MR contrasting. The obtained results characterize the coordination of Gd ions in Gd-CNPs and demonstrate new visions for controlling the optical and MR contrast properties of these nanoparticles for biomedical applications.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"37 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695541","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

Coordination chemistry of the calix[6]arene system: application in polymerisation catalysis and beyond

IF 4 3区化学

Dalton Transactions Pub Date : 2025-03-24 DOI: 10.1039/d5dt00473j

Carl Redshaw

引用次数: 0

Changing the properties of monodentate and P,C-chelating ferrocenyl-substituted 1,2,3-triazol-5-ylidene ligands through an inserted carbonyl moiety

IF 4 3区化学

Dalton Transactions Pub Date : 2025-03-24 DOI: 10.1039/d5dt00545k

Vera Varmuzova, Ivana Cisarova, Petr Štěpnička

{"title":"Changing the properties of monodentate and P,C-chelating ferrocenyl-substituted 1,2,3-triazol-5-ylidene ligands through an inserted carbonyl moiety","authors":"Vera Varmuzova, Ivana Cisarova, Petr Štěpnička","doi":"10.1039/d5dt00545k","DOIUrl":"https://doi.org/10.1039/d5dt00545k","url":null,"abstract":"Triazolylidenes derived from readily accessible triazoles are useful ligands for coordination chemistry and catalysis. This work describes the synthesis of Group 11 metal complexes of new ferrocenyl-substituted triazolylidene ligands in which the ferrocene and triazolylidene moieties are separated by a carbonyl linker. In particular, complexes of types [MCl(FcC(O){CCN(Mes)NN(Me)}-κC5)] (M = Cu or Au; Fc = ferrocenyl) and [M(FcC(O){CCN(Mes)NN(Me)}-κC5)2][BF4] (M = Cu, Ag, or Au) were prepared from FcC(O)CCH and characterised by spectroscopic methods, X-ray diffraction analysis and cyclic voltammetry. Using a similar strategy, the Pd(II) complex trans-[PdCl2(Ph2PfcC(O){CCN(Mes)NN(Me)}-κ2P,C5)] (fc = ferrocene-1,1'-diyl) was synthesised and analogously characterised. The phosphinocarbene ligand in this compound coordinates as a trans P,C-chelating ligand, unlike its analogues that lack the C=O spacer and similar compounds that combine the phosphine and carbene donor groups on the ferrocene scaffold. The influence of the carbonyl spacer was evaluated in a pair of Pd(II) bis-carbene complexes, [PdBr2({C(Fc)CN(Mes)NN(Me)}-κC5)(iPr2-bimy)] and [PdBr2(FcC(O){CCN(Mes)NN(Me)}-κC5)(iPr2-bimy)] (iPr2-bimy = 1,3-diisopropyl-1,3-dihydro-2H-benzimidazol-2-ylidene), by Huynh’s electronic parameters and the FeII/FeIII redox potential from cyclic voltammetry, which suggested an electron density decrease at the ferrocenyl group and decreased σ donor ability of the triazolylidene moiety upon introduction of the C=O linker. The Group 11 metal complexes were tested as catalysts for the metal-catalysed cyclisation of N-propargylbenzamide into 2-phenyl-5-methylene-4,5-dihydrooxazole. Among them, the chlorogold complex activated with a silver salt achieved the best results.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"21 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143677773","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

High-pressure study of barium metavanadate monohydrate

IF 4 3区化学

Dalton Transactions Pub Date : 2025-03-24 DOI: 10.1039/d5dt00423c

Daniel Errandonea, Javier Gonzalez-Platas, OUAHRANI Tarik, Fabio Piccinelli, Marco Bettinelli

{"title":"High-pressure study of barium metavanadate monohydrate","authors":"Daniel Errandonea, Javier Gonzalez-Platas, OUAHRANI Tarik, Fabio Piccinelli, Marco Bettinelli","doi":"10.1039/d5dt00423c","DOIUrl":"https://doi.org/10.1039/d5dt00423c","url":null,"abstract":"This study presents a single-crystal X-ray diffraction investigation of the high-pressure behavior of barium metavanadate monohydrate, BaV2O6·H2O, up to 7.1 GPa. These measurements were combined with high-pressure optical absorption measurements performed up to 10.1 GPa and with density-functional theory calculations. The X-ray diffraction analysis indicates that BaV2O6·H2O adopts an orthorhombic structure described by space group P212121 at ambient pressure. This structure maintains stability up to 8 GPa, in contrast to anhydrous BaV2O6 which undergoes a phase transition at 4 GPa. Throughout the pressure range examined, the compression of the crystal is highly anisotropic with the b-axis having a nearly zero linear compressibility. Additionally, our optical absorption measurements reveal that BaV2O6·H2O exhibits an indirect band gap that decreases from 4.62(5) eV at 0.03 GPa to 4.48(5) eV at 10.1 GPa. Density-functional theory calculations give similar results as the experiments and support that the decrease of the band-gap energy with pressure is caused by the enhancement of the hybridization between O 2p and V 3d state. We have also calculated the elastic constant. According to experiments and calculations BaV2O6·H2O is one of the most compressible vanadates with a bulk modulus of 33.0(5) GPa.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"3 2 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143677774","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

Development of a gold nanoparticle-based colorimetric sensor utilizing cysteine-loaded liposomes in acidic buffer solutions

IF 4 3区化学

Dalton Transactions Pub Date : 2025-03-24 DOI: 10.1039/d5dt00071h

Youkyoung Yang, Joon-Seo Park, Sang-Wha Lee

{"title":"Development of a gold nanoparticle-based colorimetric sensor utilizing cysteine-loaded liposomes in acidic buffer solutions","authors":"Youkyoung Yang, Joon-Seo Park, Sang-Wha Lee","doi":"10.1039/d5dt00071h","DOIUrl":"https://doi.org/10.1039/d5dt00071h","url":null,"abstract":"This study presents the development of a colorimetric sensing system, utilizing gold nanoparticles (AuNPs) and cysteine (Cys)-encapsulated liposomes (CELPs) as sensing probes, that functions in a variety of buffer solutions. Triton X-100 (TX-100), a nonionic surfactant, was used to simulate a biological activity that disrupts the liposome membrane. The Cys released from the CELPs by TX-100 triggered the aggregation of AuNPs, causing a noticeable red-to-blue color change, which was enhanced by Cu2+ chelation. The AuNP-CELP/TX-100 system was tested at pH 5–7.4 in various buffers. At neutral pH (7.0–7.4), the system with citrate-capped AuNPs (cit-AuNPs) displayed a distinctive colorimetric response in the presence of Cu2+ (0.3 mM), transitioning from red to blue with a UV-vis absorption shift from 525 nm to approximately 660 nm. However, the cit-AuNPs showed a limited stability in acidic buffers, and cetyltrimethylammonium bromide (CTAB)-capped AuNPs (cit-AuNPs-CTAB) were employed as an alternative at acidic pH. Overall, the AuNP-CELP/TX-100 sensing system, utilizing the cit-AuNPs-CTAB and Cu2+ chelation for Cys, exhibited the potential to be an effective sensing method working in acidic media. The test results with TX-100, which disrupts the liposome membrane, suggest that this system can be used to visualize diverse biological interactions involving membrane disruption, such as viral attacks, in acidic solutions with diverse ionic compositions.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"71 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695545","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

NHC-Ligated gold nanoparticles derived from cluster precursors for carbon monoxide oxidation reactions

IF 4 3区化学

Dalton Transactions Pub Date : 2025-03-24 DOI: 10.1039/d5dt00601e

Xiao-Ke Feng, Ren Chen, Pei-Qiong Chen, Guan-Di Wang, Peng-Chao Ren, Xiang-Kun Guo, Yujing Weng, Xi-Yan Dong

引用次数: 0

Relativistic Effect behind the Molybdenum vs. Tungsten Selectivity in Enzymes

IF 4 3区化学

Dalton Transactions Pub Date : 2025-03-24 DOI: 10.1039/d5dt00001g

Udita Das, Ankita Das, Asim Kumar Das

{"title":"Relativistic Effect behind the Molybdenum vs. Tungsten Selectivity in Enzymes","authors":"Udita Das, Ankita Das, Asim Kumar Das","doi":"10.1039/d5dt00001g","DOIUrl":"https://doi.org/10.1039/d5dt00001g","url":null,"abstract":": Molybdenum and tungsten being congeners of the 6th group of d-bock elements are similar in many respects in terms of their properties and in fact, both the molybdoenzymes and tungstoenzymes participate in similar type oxotransferase activity in their enzymes. Molybdenum is found as the heaviest essential trace metal in all forms of life but its next heavier congener, tungsten, as the heaviest metal is found only in some prokaryotic organisms. The tungstoenzymes are generally selected by nature for carrying out the low potential redox activities under the anaerobic conditions in the prokaryotic organisms. This nature’s molybdenum vs. tungsten selectivity for their biological functions under different working conditions (surrounding temperature and aerobic/anaerobic environment) is determined mainly by the relativistic effect which is experienced in different extents by these two congeners. Understanding the mechanistic aspects of the relativistic effect controlled enzymatic activities of the tungstoenzymes is of an immense biotechnological interest to develop the eco-friendly and cost effective methods of commercial synthesis of acetaldehyde through hydration of acetylene, and commercial production of hydrogen (H2, a green fuel) by producing the tungsten incorporated nitrogenase (W-N2-ase) in CA6 (mutant strain), and to develop a biomimetic method to replace the hazardous Birch reduction in organic synthesis, etc.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"215 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143677739","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

Regioselective Oxidative Bromination of Arenes by Metal-Organic Framework Confined Mono-Bipyridyl Iron(III) Catalyst

IF 4 3区化学

Dalton Transactions Pub Date : 2025-03-24 DOI: 10.1039/d5dt00443h

Rahul Kalita, Aditya Kumar, Poorvi Gupta, Bharti Rana, Bitan Sardar, Manav Chauhan, Biplab Ghosh, Yukti Monga, Kuntal Manna

{"title":"Regioselective Oxidative Bromination of Arenes by Metal-Organic Framework Confined Mono-Bipyridyl Iron(III) Catalyst","authors":"Rahul Kalita, Aditya Kumar, Poorvi Gupta, Bharti Rana, Bitan Sardar, Manav Chauhan, Biplab Ghosh, Yukti Monga, Kuntal Manna","doi":"10.1039/d5dt00443h","DOIUrl":"https://doi.org/10.1039/d5dt00443h","url":null,"abstract":"Oxidative bromination of arenes is an effective and environmentally friendly method for synthesizing bromoarenes. We have developed a highly robust zirconium-metal-organic framework (MOF)-supported mono bipyridyl-iron(III) chloride catalyst (bpy-UiO-FeCl3) for oxidative bromination of arenes using H2O2 as the oxidant and KBr as the bromine source. The bpy-UiO-FeCl3 catalyst exhibits high conversion rates for various substituted arenes, yielding significant amounts of bromoarenes with excellent regioselectivity, and recyclability under mild reaction conditions. The MOF-catalyst outperforms its homogeneous counterparts in terms of both activity and regioselectivity due to the stabilization of the mononuclear bipyridyl-iron(III) species within the active sites in the MOF's pores. Furthermore, the confinement of these active sites within the robust, well-defined, and uniform porous framework enhances the regioselectivity of the bromination through shape-selective catalysis. The mechanism of bpy-UiO-FeCl3 catalyzed oxidative bromination of arenes was thoroughly investigated by a combination of control experiments, spectroscopic analyses, and computational studies. These findings underscore the importance of MOFs in the development of heterogeneous catalysts based on earth-abundant metals for the sustainable synthesis of haloarenes.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"9 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143677775","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