Dalton Transactions最新文献

{"title":"The Bonding Situations in Ruthenium Chalcogenonitrosyl Compounds: A Physical Reasoning","authors":"Richard Fragnani Cardoso, Vinícius Acir Glitz, Renato Luis Tame Parreira, Giovanni Finoto Caramori, Luis Henrique Silveira Lacerda","doi":"10.1039/d4dt02680b","DOIUrl":"https://doi.org/10.1039/d4dt02680b","url":null,"abstract":"This research presents, for the first time, a comprehensive and rigorous investigation of ruthenium(II) chalcogenonitrosyl bonding situations in two sets of coordination compounds: [Ru(NE)Cl<small>₂</small>(L_{OEt})] (<strong>1a</strong>-<strong>4a</strong>) and [Ru(NE)Cl<small>₂</small>(L_{OEt})]<small>^-</small> (<strong>1b</strong>-<strong>4b</strong>), where E = O, S, Se, Te. Prior to and following the monoelectronic reduction, the Ru-NE bonding situations were subjected to analysis. The calculated geometric parameters indicate that both the Ru-NE and N-E bond lengths are susceptible to variation depending on the nature of the chalcogen employed. Furthermore, the results demonstrate that the monoelectronic reduction process serves to diminish the N=E double bond character. The generalized Kohn-Sham energy decomposition analysis (GKS-EDA) was conducted to illustrate the Ru-NE bonding scenarios prior to and following the monoelectronic reduction. The results provide valuable insights into the nature of Ru(II)-NE (E = O, S, Se, Te) bonds, the influence of chalcogens on ruthenium compounds, as well as how the monoelectronic reduction affects the release of NE groups. The main findings indicate that the total interaction energy, prior to the monoelectronic reduction, is three to four times more stabilizing than in the reduced analogs, confirming that the reduction unequivocally enhances the lability of the Ru-NE bond even when heavier chalcogen analogues are employed.","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":"142597368","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":"Titanosiloxanes Consisting of Tetrahedrally Coordinated Ti Cores and Branched Siloxane Cages","authors":"Shohei Saito, Kenta Kawamura, Naoto Sato, Takamichi Matsuno, Hiroaki Wada, Kazuyuki Kuroda, Atsushi Shimojima","doi":"10.1039/d4dt02848a","DOIUrl":"https://doi.org/10.1039/d4dt02848a","url":null,"abstract":"Well-defined titanosiloxane molecules with tetrahedrally coordinated Ti centers are synthesized by using mono-silanol functionalized siloxane cages as building blocks. The Ti sites are modified with the OSi(OSi)3 units, which is analogous to that of Ti-containing zeolites. Such titanosiloxane molecules are important as models for Ti-containing silica-based catalysts.","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":"142598214","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":"Development of Polyoxometalate-loaded MOF for Heterogeneous Catalysis and Enhanced Dye Adsorption","authors":"Ketan Maru, Sarita Kalla, Ritambhara Jangir","doi":"10.1039/d4dt02645d","DOIUrl":"https://doi.org/10.1039/d4dt02645d","url":null,"abstract":"The study focuses here on the enhancement of MIL-117 functionality by incorporating well-known polyoxometalate (POM); tetrabutylammonium octamolybdate [(n-C4H9)4N]4[Mo8O26]. Using an encapsulation method with conventional heating, Mo8O264- anions were first time successfully integrated into the MIL-117 tubular channels (Mo8O26@MIL-117). Comprehensive characterization of the material through FTIR, XRD, BET, FE-SEM, EDX, and XPS confirmed the uniform distribution of Mo8O264- within MIL-117 without compromising its structural integrity. The Mo8O26@MIL-117 composite demonstrates exceptional catalytic performance in oxidative C-N bond formation and Paal-Knorr pyrrole synthesis, achieving high yields under optimized conditions with diverse amine substrates. Characterization and stability assessments confirm Mo8O26@MIL-117 as a robust and recyclable catalyst, maintaining structural integrity and catalytic activity over multiple cycles, highlighting its potential for sustainable applications in synthetic chemistry. The composite material was also evaluated for its efficacy in dye removal, specifically targeting Methylene blue (MB) and Rhodamine B (RHB) from aqueous solutions. Mo8O26@MIL-117 exhibited superior adsorption capacity for MB compared to MIL-117 alone, demonstrating high efficiency even at elevated concentrations. The composite showed improved selectivity towards MB over RHB, highlighting its potential for selective dye removal in wastewater treatment 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":"142598215","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":"Cationic first-row transition metal saccharinate complexes with tris(2-pyridylmethyl)amine: Synthesis, structures and anticancer studies","authors":"Ceyda Icsel, Seyma Aydinlik, Muhittin Aygün, Veysel T. Yilmaz","doi":"10.1039/d4dt02258k","DOIUrl":"https://doi.org/10.1039/d4dt02258k","url":null,"abstract":"A series of new cationic first-row transition metal complexes of [Mn(sac)(H2O)(tpma)](sac)H2O (Mn), [(µ-O){FeCl(tpma)}2](sac)23H2O (Fe), [Co(sac)(H2O)(tpma)](sac)H2O (Co), [Ni(H2O)2(tpma)](sac)22H2O (Ni), [Cu(sac)(tpma)](sac) (Cu) and [Zn(sac)(H2O)(tpma)](sac) (Zn), where sac = saccharinate and tpma = tris(2-pyridylmethyl)amine, were synthesized and structurally characterized by elemental analysis, UV-Vis, IR, ESI-MS, NMR, X-ray diffraction and conductivity measurements. The cytotoxic activity of the metal complexes was evaluated in vitro against lung carcinoma (A549), breast adenocarcinoma (MCF7), colon (HT29), and normal BEAS-2B cell lines. Mn and Fe displayed potent cytotoxic activity in all cell lines with IC50 values between 1.99 ± 0.33 and 6.65 ± 0.67 μM, while Cu moderately affected the growth of HT29 cells. However the rest of the metal complexes did not demonstrated any growth inhibitory effect. Further studies with Fe treated HT29 cells through cellular imaging analysis indicated that Fe significantly induced intracellular ROS (reactive oxygen species) accumulation, mitochondrial dysfunction and double-strand DNA breaks, and eventually caused apoptotic cell death through the intrinsic pathway.","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":"142598213","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":"Modular synthesis of triphenylphosphine-derived cage ligands for rhodium-catalyzed hydroformylation applications","authors":"Wenlong Wang, Cunyao Li, Wenhao Wang, Yuqin Qiu, Jinlong Lu, Hongguang Liu, Yizhou Zhan, Li Yan, Yunjie Ding","doi":"10.1039/d4dt02627f","DOIUrl":"https://doi.org/10.1039/d4dt02627f","url":null,"abstract":"Four new triphenylphosphine-derived cage ligands were modularly synthesized via dynamic imine chemistry (DIC), and their absolute structures were characterized by sigle crystal X-ray diffraction (SXRD), nuclear magnetic resonance (NMR) and high resolution mass spectrum (HRMS). In contrast to small-molecule analogues, cage ligands demonstrate superior activity and selectivity. The Rh/Cage-L2 catalyst exhibits remarkable performance with an aldehyde selectivity of 89%, accompanied by a TOF value of 2665 h-1 and an l/b ratio of 2.60, thereby showcasing leading activity, chemical selectivity, and regioselectivity in the realm of homogeneous catalysts that rely on triphenylphosphine ligands. The reason for the formation of a higher l/b ratio, with a 3.84 kJ·mol-1 difference in the energy of the rate-determining step, has been explained through density functional theory (DFT) calculations. In addition, a Janus-type PPh3-Au complex has been discovered during the study of the coordination of cage ligands, offering partial corroboration for the single coordination mechanism of these cage ligands. The large steric hindrance effect of cage ligands is believed to play a pivotal role in the hydroformylation reaction. This work highlights the potential application of cage ligands and inspires future efforts in the search of highly selective and efficient organometallic catalysts.","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":"142597369","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":"Hydrate of neutral iron(III) complex based on pyruvic acid thiosemicarbazone ligand with abrupt spin-crossover with T1/2=340 K and wide hysteresis loop of 45 K","authors":"Maxim Andreevich Blagov, Alexander V. Akimov, Anatoly S Lobach, Leokadiya Zorina, Sergey Simonov, Konstantin Zakharov, Alexander Vasiliev, Natalia Spitsyna","doi":"10.1039/d4dt02901a","DOIUrl":"https://doi.org/10.1039/d4dt02901a","url":null,"abstract":"The hydrate of neutral iron(III) complex based on pyruvic acid thiosemicarbazone ligand [Fe<small>^III</small>(Hthpy)(thpy)]·H<small>₂</small>O (<strong>1</strong>) was synthesized and characterized using FT-IR spectroscopy, powder and single-crystal X-ray diffraction, <em>dc</em> magnetic measurements, EPR and <small>⁵⁷</small>Fe Mössbauer spectroscopy. The crystal structure of <strong>1</strong> was determined for the first time. Two distinct chelating ligands Hthpy<small>^ˉ</small> and thpy<small>^2ˉ</small>coordinate the Fe(III) ion to form the FeN<small>₂</small>O<small>₂</small>S<small>₂</small> octahedron which shows a low spin geometry at 150-350 K. The crystal packing contains infinite chains of the Fe(III) complexes as well as water molecules located in cavities. Along the chain, π-π interacting pairs of the Fe complexes are linked by H-bonding. According to the <em>dc</em> magnetic measurements, the complete abrupt spin-crossover with half-transition temperature T<small>_1/2</small>=340 K and a hysteresis loop of 45 K occurs in the temperature range of 300‒363 K. Based on the X-ray structure of <strong>1</strong>, the Bleaney–Bowers equation for the isolated dimer model was used to approximate the temperature dependence of the magnetic susceptibility in the range of 2–50 K. The defined intradimer exchange constant <em>J<small>_exp</small></em>= −0.498(1) K corresponds to a weak antiferromagnetic exchange between the iron(III) magnetic centers. DFT calculations of H- and π-π bonded fragments of the crystal structure of <strong>1</strong> in the HS and LS states were carried out. Moreover, BS-DFT calculations confirm the presence of antiferromagnetic exchange <em>J<small>_calc</small></em> = – 0.92 K in the π-π bonded pairs of the ferric complexes, and show the exchange pathway between Fe(III) ions by the calculated spin density distribution.","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":"142597814","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":"Synthesis of Organo-uranium(II) Species in the Gas-phase using Reactions Between [UH]+ and Nitriles","authors":"Justin Terhorst, Theodore A. Corcovilos, Samuel J. Lenze, Michael J. van Stipdonk","doi":"10.1039/d4dt02508c","DOIUrl":"https://doi.org/10.1039/d4dt02508c","url":null,"abstract":"One challenge in the quest to map the intrinsic reactivity of model actinide species has been the controlled synthesis of organo-actinide ions in the gas phase. We report here evidence that a series of gas-phase, σ-bonded [U-R]+ species (where R = CH3, C2H3, C2H5, C3H7, or C5H6) can be generated for subsequent study of ion-molecule chemistry by using preparative tandem mass spectrometry (PTMSn) via ion-molecule reactions between [UH]+ and a series of nitriles. Density functional theory calculations support the hypothesis that the [U-R]+ ions are created in a pathway that involves intramolecular hydride attack and the elimination of neutral HCN. Subsequent reactivity experiments revealed that the [UCH3]+ readily undergoes hydrolysis, yielding cationic uranium hydroxide ([UOH]+) and methane (CH4). Other possible reaction pathways, such as the spontaneous rearrangement to [HU=CH2]+, are shown by theoretical calculations to have energy barriers, strengthening the evidence for the formation of a σ-bonded [U-CH3]+ complex in the gas-phase.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142594263","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":"Alkyl initiated ring opening polymerization of lactide by indium complexes supported by NCN pincer ligands","authors":"Takeo Iwase, Afagh Habibzadeh, Chatura Goonesinghe, Kudzanai Nyamayaro, Joseph Chang, Jason Wai-Lok Poon, Salik Hasan Rushdy, Justin Koh, Brian O. Patrick, Parisa Mehrkhodavandi","doi":"10.1039/d4dt02603a","DOIUrl":"https://doi.org/10.1039/d4dt02603a","url":null,"abstract":"Indium-alkyl NCN pincer complexes supported by amine and imine donors are active catalysts for the ring opening polymerization of lactide. The amine indium complexes are significantly more active for polymerization due to the decoordination of the amine donors at higher temperatures. Solid state structures of the imine and amine indium complexes indicate that the imine–indium bonds are stronger than the analogous amine–indium bonds. Higher molecular weight polymers that were not observable by MALDI-TOF were shown to be linear by comparing their intrinsic viscocities with those of known linear polymers. The alkyl indium complexes are more active than the analogous alkyl aluminum complexes but are prone to transesterification reactions.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142594262","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":"Solvent-dependent Ln(III) clusters assembled by immobilization of CO2 in the air: zero-field single-molecule magnets and magnetic refrigerant materials","authors":"Cai-Ming Liu, Xiang Hao, Zhao-Bo Hu, He-Rui Wen","doi":"10.1039/d4dt02310b","DOIUrl":"https://doi.org/10.1039/d4dt02310b","url":null,"abstract":"The automatic fixation of CO<small>₂</small> in the air plays a key role in the construction of Dy(III) single-molecule magnets (SMMs) and Gd(III) magnetic refrigeration molecular materials using Ln(III)Cl<small>₃</small> (Ln = Dy and Gd) and a new hydrazone Schiff base ligand {H<small>₂</small>L = (E)-N'-(4-fluoro-2-hydroxybenzylidene)pyrimidine-4-carbohydrazide}, which is condensed from pyrimidine-4-carbohydrazide and 4-fluorosalicylaldehyde. Surprisingly, the small differences in methanol and ethanol solvents lead to dramatic changes in the structures of Ln(III) cluster complexes. When methanol and ethanol participated in the reaction, a trapezoidal pyramid Dy(III) pentanuclear cluster [Dy<small>₅</small>L<small>₅</small>(OH)<small>₂</small>(CO<small>₃</small>)(O<small>₂</small>COMe)(MeOH)<small>₃</small>(H<small>₂</small>O)]⸱3MeOH·3.5H<small>₂</small>O (<strong>1</strong>) and a triangular prism Dy(III) hexanuclear cluster [Dy<small>₆</small>L<small>₆</small>(CO<small>₃</small>)<small>₂</small>(EtOH)<small>₂</small>(H<small>₂</small>O)<small>₂</small>(Cl)<small>₂</small>]⸱6EtOH were obtained, respectively; and a tub-like Gd(III) octanuclear cluster [Gd<small>₈</small>L<small>₈</small>(CO<small>₃</small>)<small>₄</small>(MeOH)<small>₃</small>(H<small>₂</small>O)<small>₅</small>]⸱12MeOH·3CH<small>₂</small>Cl<small>₂</small>·3.25H<small>₂</small>O (<strong>3</strong>) for methanol and a trapezoidal pyramid Gd(III) pentanuclear cluster [Gd<small>₅</small>L<small>₄</small>(HL)(CO<small>₃</small>)(O)(OH)(EtOH)<small>₅</small>(H<small>₂</small>O)<small>₂</small>(Cl)]⸱EtOH⸱3H<small>₂</small>O (<strong>4</strong>) for ethanol were yielded. Notably, complex <strong>1</strong> contains not only the carbonate anion but also the monomethyl carbonate anion as bridging ligands, which are formed by immobilizing CO<small>₂</small> in the air, while complexes <strong>2</strong>, <strong>3</strong> and <strong>4</strong> contain the carbonate bridging ligand only. Magnetic properties’ investigations revealed that both <strong>1</strong> and <strong>2</strong> are zero-field SMMs, with U<small>_eff</small>/k values of 93.2 K and 133.5 K, respectively; while <strong>3</strong> and <strong>4</strong> show large magnetocaloric effects, with the largest −ΔS<small>_m</small> values of 27.52 Jkg<small>^–1</small>K<small>^–1</small> at 2.0 K for ΔH = 7 T for<strong> 3</strong> and 27.58 Jkg<small>^–1</small>K<small>^–1</small> at 2.5 K for ΔH = 7 T for <strong>4</strong>.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142589123","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":"Mechanistic studies of NOx reduction reactions involving metal complexes: encouragement of DFT calculations","authors":"Yohei Kametani, Yoshihito Shiota","doi":"10.1039/d4dt02420f","DOIUrl":"https://doi.org/10.1039/d4dt02420f","url":null,"abstract":"The reduction of nitrogen oxides (NOx), which is mainly mediated by metalloenzymes and metal complexes, is a critical process in the nitrogen cycle and environmental remediation. This Frontier article highlights the importance of density functional theory (DFT) calculations to gain mechanistic insights into nitrite (NO2−) and nitric oxide (NO) reduction reactions facilitated by copper complexes by focusing on two key processes: the reduction of NO2− to NO by a monocopper complex, with special emphasis on the concerted proton–electron transfer, and the reduction of NO to N2O by a dicopper complex, which involves N–N bond formation, N2O2 isomerization, and N–O bond cleavage.. These findings underscore the utility of DFT calculations in unraveling complicated reaction mechanisms and offer a foundation for future research aimed at improving the reactivity of transition metal complexes in NOx reduction reactions.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142589122","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}