Dalton Transactions最新文献

{"title":"Highly selective organo-gallium hydroxamate mediated inhibition of antibiotic resistant Klebsiella pneumoniae","authors":"Rebekah N. Duffin, Jenisi Kelderman, Megan Herdman, Philip Craig Andrews","doi":"10.1039/d4dt02440k","DOIUrl":"https://doi.org/10.1039/d4dt02440k","url":null,"abstract":"Five complexes of gallium derived from hydroxamic acids have been synthesised, characterised, and their anti-bacterial activity and mammalian cell toxicity established. These are three metal-organic complexes; [Ga(BPHA]<small>₃</small> 1, [Ga(BHA-H]<small>₃</small> 2, [Ga(SHA-H<small>₂</small>)(SHA-H)]<small>₃</small> 3, and two heteroleptic organometallic complexes [GaMe<small>₂</small>(BPHA)] 4, and [GaMe(BHA-H)<small>₂</small>] 5, along with the iron complex [Fe(BPHA)<small>₃</small>] 6 (BPHA-H = N-benzoyl-N-phenylhydroxamic acid, BHA-H2 = phenylhydroxamic acid, and SHA-H3 = salicylhydroxamic acid). Solid-state structures of 1, 4 – 6 were identified by single-crystal X-ray crystallography. Complexes 1 and 6 adopt an octahedral geometry at the metal centre, while the organometallic complexes 4 and 5 adopt, respectively, tetrahedral and trigonal bipyramidal geometry. The solution and solid-state chemistry of complex 3 was found to differ: the solution state is composed of an equilibrium mixture of the bis-complexed hydroximate-hydroxamate species and the homoleptic tris-hydroxamate species, with the solid state preferring the bis-complexed hydroximate-hydroxamate composition. The methyl gallium complexes 4 and 5 differed in their preferred composition with 4 forming the expected dimethyl hydroxamate complex while 5 stabilises as the methyl bis-hydroxamate complex. Complexes were tested for the anti-microbial activity against a series of Gram-positive and Gram-negative bacteria, with an emphasis on the Gram-negative Klebsiella pneumoniae. While the metal-organic complexes 1, 2, 3 and 6 showed little to no activity towards either the bacteria or mammalian cells, the alkyl gallium complexes 4 and 5 were found to have exceptional activity toward K. pneumoniae in RPMI-HS media with MIC values of 78 nM. Interestingly, [GaMe<small>₂</small>(OH)] also showed significant activity with an MIC of 156 nM.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142600027","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}

{"title":"β-Cyclodextrin and cucurbit[7]uril as protective encapsulation agents of the CO-releasing molecule [CpMo(CO)3Me]","authors":"Rodrigo P. Monteiro, Isabel B. Calhau, Ana C. Gomes, André D. Lopes, José P. Da Silva, Isabel S. Gonçalves, Martyn Pillinger","doi":"10.1039/d4dt01863j","DOIUrl":"https://doi.org/10.1039/d4dt01863j","url":null,"abstract":"The CO releasing ability of the complex [CpMo(CO)<small>₃</small>Me] (<strong>1</strong>) (Cp = η<small>⁵</small>-C<small>₅</small>H<small>₅</small>) has been assessed using a deoxymyoglobin-carbonmonoxymyoglobin assay. In the dark, CO release was shown to be promoted by the reducing agent sodium dithionite in a concentration-dependent manner. At lower dithionite concentrations, where dithionite-induced CO release was minimised, irradiation at 365 nm with a low-power UV lamp resulted in a strongly enhanced release of CO (half-life (<em>t</em><small>_1/2</small>) = 6.3 min), thus establishing complex <strong>1</strong> as a photochemically activated CO-releasing molecule. To modify the CO release behaviour of the tricarbonyl complex, the possibility of obtaining inclusion complexes between <strong>1</strong> and β-cyclodextrin (βCD) or cucurbit[7]uril (CB7) by liquid–liquid interfacial precipitation (<strong>1</strong>@βCD(IP)), liquid antisolvent precipitation (<strong>1</strong>@CB7), and mechanochemical ball-milling (<strong>1</strong>@βCD(BM)) was evaluated. All these methods led to the isolation of a true inclusion compound (albeit mixed with nonincluded <strong>1</strong> for <strong>1</strong>@βCD(BM)), as evidenced by powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), FT-IR and FT-Raman spectroscopies, and <small>¹³</small>C{<small>¹</small>H} magic angle spinning (MAS) NMR. PXRD showed that <strong>1</strong>@βCD(IP) was microcrystalline with a channel-type crystal packing structure. High resolution mass spectrometry studies revealed the formation of aqueous phase 1 : 1 complexes between <strong>1</strong> and CB7. For <strong>1</strong>@βCD(IP) and <strong>1</strong>@CB7, the protective effects of the hosts led to a decrease in the CO release rates with respect to nonincluded <strong>1</strong>. βCD had the strongest effect, with a <em>ca.</em> 10-fold increase in <em>t</em><small>_1/4</small> for dithionite-induced CO release, and a <em>ca.</em> 2-fold increase in <em>t</em><small>_1/2</small> for photoinduced CO release.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142600028","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}

{"title":"Stable homogeneous silver(I) catalysts for the highly efficient cycloaddition of azides onto terminal alkynes in water","authors":"Meysam Kakavand, Anna Kozakiewicz, Abdollah Neshat","doi":"10.1039/d4dt02825b","DOIUrl":"https://doi.org/10.1039/d4dt02825b","url":null,"abstract":"To develop stable and efficient silver(I) catalysts and evaluate the role of sulfur and phosphorus donor ligands in the catalytic cycloaddition of selected organic azides and alkynes (AAC), a series of mononuclear Ag(I) and heteronuclear Ag(I)-Fe(II) complexes were synthesized. The synthesis utilized phosphine and sulfur donors from the dialkyldithiophosphate and borate families, specifically Na[S2H2B(mt)2]. These complexes are designated as [(dppf)AgSP(S)(OiPr)2] (1), [S2H2B(mt)2Ag(-dppf)Ag(S2H2B(mt)2] (2), [(dppf)Ag(-dppf)Ag(dppf)] (3), and [(dppe)AgS2H2B(mt)2] (5). The complexes 1-5 were characterized using a combination of 1H, 13C{1H}, and 31P{1H} NMR spectroscopy, as well as IR spectroscopy techniques. In two instances, single-crystal X-ray diffraction analysis was also employed. Complex 3 exhibited high catalytic activity and regioselectivity in the cycloaddition reaction conducted in water at 40 °C.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142600029","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}

{"title":"Indium-Catalyzed Hydrosilylation of Nitroarenes to Aromatic Amines","authors":"Sai Kumar Gobbilla, Kulsum Bano, Priyabrata Biswal, Soumyadip Dey, Ravi Kumar, Abhijit Sau, Vadapalli Chandrasekhar, Tarun Kanti Panda","doi":"10.1039/d4dt02861a","DOIUrl":"https://doi.org/10.1039/d4dt02861a","url":null,"abstract":"Herein, we report the synthesis of three indium complexes (1-3) supported by different chelating ligands (L1-L3). The indium metal complexes were characterized by using multinuclear NMR, and their solid-state structures were confirmed by single-crystal X-ray crystallography. The indium complex 1 (5 mol%) effectively reduced nitroarenes in the presence of phenylsilane and NaI. Nitroarenes containing different functionalities were reduced under standard conditions to give the corresponding amines in good yields.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142600046","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}

{"title":"Fe/Fe3C particles encapsulated in hollow carbon nanoboxes for high performance zinc–air batteries","authors":"Chuyun Huang, Wenyuan Zhang, Xuezhi Hu, Shiliang Fei, Fhulufhelo Nemangwele, Nnditshedzeni Eric Maluta, Yangsen Hu, Hui Lv, Pei Hu, Zhuo Peng","doi":"10.1039/d4dt02396j","DOIUrl":"https://doi.org/10.1039/d4dt02396j","url":null,"abstract":"Zinc–air batteries are recognized for their environmental friendliness and high energy density; however, the slow kinetics of the oxygen reduction reaction (ORR) at the air electrode hinder their commercial viability. The research focuses on synthesizing cubic hollow carbon structures derived from Metal–Organic Frameworks (MOFs), which enhance catalytic performance through improved conductivity and mass transfer. The resulting Fe/Fe<small>₃</small>C/HCNB catalyst demonstrates a half-wave potential of 0.826 V for ORR and achieves a peak power density of 274 mW cm<small>⁻²</small> in zinc–air batteries, surpassing commercial Pt/C catalysts. Electrochemical impedance spectroscopy reveals that the hollow structure enhances hydrophilicity and reduces solution resistance, facilitating greater active site engagement in electrochemical reactions. The study concludes that the unique structural features of Fe/Fe<small>₃</small>C/HCNB significantly improve discharge performance and stability, positioning it as a promising alternative for zinc–air battery applications.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142597815","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}

{"title":"Investigating the formation of metal nitride complexes employing a tetradentate bis-carbene bis-phenolate ligand","authors":"Romain Kunert, Diego Martelino, Samyadeb Mahato, Nicholas Hein, Jason Pulfer, Christian Philouze, Olivier Jarjayes, Fabrice Thomas, Tim Storr","doi":"10.1039/d4dt01765j","DOIUrl":"https://doi.org/10.1039/d4dt01765j","url":null,"abstract":"The synthesis of MnV and CrV nitride complexes of a pro-radical tetradentate bis-phenol bis-N-heterocyclic carbene ligand H2LC2O2 were investigated. Employing either azide photolysis of the MnIII precursor complex MnLC2O2(N3) or a nitride exchange reaction between MnLC2O2(Br) and the nitride exchange reagent Mnsalen(N) failed to provide a useful route to the target nitride MnLC2O2(N). Experimental results support initial formation of the target nitride MnLC2O2(N), however, the nitride rapidly inserts into a Mn-C<small>_NHC</small> bond. A second insertion reaction results in the isolation of the doubly inserted ligand product [H2LC2O2(N)]+ in good yield. In contrast, the Cr analogue CrLC2O2(N) was readily prepared and characterized by a number of experimental methods, including X-ray crystallography. Theoretical calculations predict a lower transition state energy for nitride insertion into the M-CNHC bond for Mn in comparison to Cr, and in addition the N-inserted product is stabilized for Mn while destabilized for Cr. Natural bond order (NBO) analysis predicts that the major bonding interaction (π MN to σ* M-CNHC) indicates nucleophilic attack of the nitride on the carbene. Finally, one-electron oxidation of CrLC2O2(N) affords a relatively stable cation that is characterized by experimental and theoretical analysis to be a metal-oxidized d0 CrVI species.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142597365","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}

{"title":"Bicyclic (Alkyl)(Amino)Carbenes (BICAACs): Synthesis, Characteristics, and Applications","authors":"Ankita Sharma, Unnikrishnan Nair K, Subrata Kundu","doi":"10.1039/d4dt02696a","DOIUrl":"https://doi.org/10.1039/d4dt02696a","url":null,"abstract":"Carbenes in general and isolable NHCs (N-heterocyclic carbenes) in particular have been useful ligands in recent years. The emergence of CAACs [cyclic(alkyl)(amino)carbenes], BICAACs [bicyclic(alkyl)(amino)carbenes], and many other carbenes has marked revolutionary milestones in this field. These carbenes possess an intriguing blend of highly electrophilic and nucleophilic characteristics, owing to their remarkably narrow HOMO-LUMO energy gap. The isolation and characterization of these carbenes hold significance not only due to their fascinating electronic properties but have demonstrated their prowess across various domains, including isolation of transition metal complexes, medicinal applications, catalysis, and radical stabilization. While the chemistry of 5-membered NHCs and CAACs have been extensively explored, the investigation of BICAAC has just begun. This review covers the synthesis, characterization, and reactivity of BICAACs, and outlines diverse applications of BICAACs in organometallic, metal-free catalysis, and main-group chemistry.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142597817","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}

{"title":"Activation of small molecules by ambiphilic NHC-stabilized phosphinoborenium cation: formation of boreniums with B-O-C, B-O-B, and B-O-P structural motifs","authors":"Tomasz Wojnowski, Anna Ordyszewska, Hanna Halenka, Iwona Anusiewicz, Jarosław Chojnacki, Kinga Kaniewska-Laskowska, Rafał Grubba","doi":"10.1039/d4dt02656j","DOIUrl":"https://doi.org/10.1039/d4dt02656j","url":null,"abstract":"The reactivity of the phosphinoborenium cation supported by a 1,3,4,5-tetramethylimidazolin-2-ylidene ligand toward small molecules was explored. The phosphinoborenium cation exhibited dual Lewis acid–base properties due to the presence of the Lewis acidic boron center and the Lewis basic phosphido ligand connected by a covalent bond. The reaction of the title cation with CO<small>₂</small> led to the insertion of a CO<small>₂</small> molecule into the P-B bond. The obtained borenium CO<small>₂</small>-adduct underwent hydrolysis, forming an N-heterocyclic carbene stabilized diborenium dication bearing a B-O-B functionality. The activation of N<small>₂</small>O proceeded via the insertion of an oxygen atom into the B-P bond of the parent cation, yielding a borenium cation with a phosphinite moiety. An alternative synthetic pathway to borenium cations with a B-O-P skeleton was achieved via the activation of secondary phosphine oxides by the phosphinoborenium cation. Furthermore, borenium cations and diborenium dications with B-O-C structural motifs were obtained from the reaction of the title compound with perfluorinated tert-butyl alcohol and hydroquinone, respectively. The structure of the obtained borenium cations is discussed based on multinuclear NMR spectroscopy, X-ray diffraction, and density functional theory calculations.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142597816","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}

{"title":"Solvatomorphic Phase Transitions and Tunable Luminescence Emission in Lanthanide Metal-Organic Frameworks","authors":"Alena A. Vasileva, Pavel A. Demakov, Tatiana Y. Guselnikova, Alexey A. Ryadun, Vladimir P Fedin, Danil N. Dybtsev","doi":"10.1039/d4dt02613f","DOIUrl":"https://doi.org/10.1039/d4dt02613f","url":null,"abstract":"Four new metal-organic frameworks with the formulae [Sm<small>₂</small>(phen)<small>₂</small>(NO<small>₃</small>)<small>₂</small>(chdc)<small>₂</small>]·2Solv, where Solv = N,N-dimethylformamide (DMF; <strong>1</strong>), N,N-dimethylacetamide (DMA; <strong>2</strong>), N,N-diethylformamide (DEF; <strong>3</strong>), N-formylpiperidine (NFP; <strong>4</strong>), phen = 1,10-phenanthroline and chdc<small>^2–</small> = <em>trans</em>-1,4-cyclohexanedicarboxylate were synthesized and structurally characterized. These compounds are based on similar binuclear samarium(III)-carboxylate blocks, bound by flexible chdc linker into layered sql-type coordination networks. Different amide solvents drive different intralayer block orientations between <strong>1</strong> and <strong>2</strong>–<strong>4</strong> and different layer-to-layer packings in all the described compounds. A strong dependence of the emission color upon varying excitation wavelength was determined for <strong>1</strong>–<strong>4</strong>, while relative impacts of Sm<small>³⁺</small> and phen emission into overall luminescence were found to depend strongly on these packings, and their reasonable correlation to the distances between closest π-π-stacked phen moieties in the structures was revealed. Phase transitions between compounds <strong>1</strong>–<strong>4</strong> were studied by means of powder X-ray diffraction. Additionally, two-metal near-white luminophores were obtained for phases <strong>3</strong> and <strong>4</strong> by doping their synthetic systems by minor (~5%) additive of Tb<small>³⁺</small>. In general, this study shows a possibility of tuning the luminescence properties of porous metal-organic frameworks by minor structural differences induced by solvent-driven dynamics with no apparent quenching or other direct impact of the optical properties of the solvent included.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142597366","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}

{"title":"Construction of efficient Pb(II) carboxylate catalysts for Oxygen and Hydrogen Evolution Reactions","authors":"Janak ., Vijay Sarjerao Sapner, Bhaskar Ramchandra Sathe, Sadhika Khullar","doi":"10.1039/d4dt02958e","DOIUrl":"https://doi.org/10.1039/d4dt02958e","url":null,"abstract":"The development of cost-effective and efficient electrocatalysts can solve the problem in the production of energy via water splitting reactions. In this work, we focused on two lead-based coordination polymers (CPs) {[Pb2(TPBN)(HBTC)2]2⸱5H2O}n (CP1), and {[Pb2(TPBN)(NDC)2].H2O}n (CP2) that are synthesized by the self-assembly method at room temperature in good yields. Two dimensional structures of CP1 and CP2 were determined by the single crystal X-ray diffraction. Their phase purity and thermal stability were reconfirmed by powder diffraction and TGA analysis, respectively. In addition to this, Hirshfeld surface analysis of CP1 and CP2 also exhibits the key differences in the intermolecular interactions of both the CPs. Both CP1 and CP2 were employed for the HER and OER. It has been found that the change in the carboxylate from BTC to NDC resulted in better electrocatalytic activity towards water splitting reaction. This may be attributed to the presence of more π character in NDC as compared to BTC which makes the electron flow much easier for the HER process. CP1 and CP2 shows an overpotential values of 580 mV, and 550 mV, respectively, in 1 M H2SO4 to reach 10 mA cm−2 current density with Tafel slope of 31 mV dec−1, and 25 mV dec−1, respectively. For the OER process, CP1 and CP2 exhibit an overpotential of 590 mV and 470 mV, respectively, in 1 M KOH at a current density of 50 mA cm−2 with Tafel slope values of 56 mV dec−1, and 81 mV dec−1, respectively. Turnover frequency (TOF) of CP1 and CP2 as 1.05 s−1 and 3.21 s−1 for OER and 1.97 s−1 and 9.65 s−1, for HER, respectively.These results indicate that both CPs can act as highly efficient electrocatalysts for the clean energy production.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142598210","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}