European Journal of Inorganic Chemistry最新文献

{"title":"(P,N,P)Pd- versus (P,N,P)Ni-Catalyzed Suzuki-Miyaura Cross-Coupling Reactions under Green Conditions†","authors":"Vincent Fagué,&nbsp;Diogo Dos Santos,&nbsp;Jean-Claude Daran,&nbsp;Sonia Mallet-Ladeira,&nbsp;Pascal Guillo,&nbsp;Christophe Fliedel","doi":"10.1002/ejic.202400729","DOIUrl":"https://doi.org/10.1002/ejic.202400729","url":null,"abstract":"<p>Palladium dichloride (<b>6</b>-<b>10</b>) and nickel dichloride (<b>11</b>-<b>15</b>) complexes of a series of <i>N</i>-substituted/functionalized bis(diphenylphosphino)amine-type ligands (<b>1</b>-<b>5</b>) were synthesized and characterized, using multinuclear NMR and FT-IR spectroscopic techniques, mass spectrometry and elemental analysis. The solid-state structures of two palladium(II) (<b>6</b> and <b>8</b>⋅2CHCl₃) and two nickel(II) (<b>12</b> and <b>15</b>) complexes could be confirmed by single-crystal X-ray diffraction studies. All the complexes were evaluated as catalysts in the Suzuki-Miyaura cross-coupling reaction. Applying what appeared, from the literature, as the optimized reaction conditions for such complexes, <i>i. e</i>. Cs₂CO₃ as base and 1,4-dioxane as solvent, the palladium catalysts were found very efficient for the coupling of phenylboronic acid and aryl bromides functionalized with weak and moderate electron donating groups (EDGs) and weak and moderate electron withdrawing groups (EWGs). In contrast, reduced activity was observed for aryl bromides functionalized with strong EDGs and EWGs and no activity for aryl chlorides. Under the same reaction conditions, the nickel catalysts were completely inactive. Applying different and “greener” reaction conditions, <i>i. e</i>. K₃PO₄ as base and <i>tert</i>-amyl alcohol as solvent, the nickel catalysts efficiently converted various aryl bromides and chlorides with a pool of aryl boronic acids, therefore clearly surpassing their palladium analogues at lower cost, economically and environmentally. Surprisingly, these reaction conditions could also be successfully applied to the palladium complexes, improving their performances (activity towards aryl chlorides) and offering a “greener” alternative to the common conditions.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 6","pages":""},"PeriodicalIF":2.2,"publicationDate":"2025-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202400729","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143489883","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synthesis, Characterisation, and Catalytic Evaluation of Ru-ONO Complexes Featuring N- and P-Based Ligands","authors":"Babatunde Awe,&nbsp;Glendin Swart,&nbsp;Elizabeth Erasmus,&nbsp;Frederick P. Malan","doi":"10.1002/ejic.202400619","DOIUrl":"https://doi.org/10.1002/ejic.202400619","url":null,"abstract":"<p>Nine new ruthenium complexes featuring nitrogen and phosphorus donor ligands were synthesised from a Ru precursor featuring a rigid ONO-pincer ligand. The choice of nitrogen- and phosphorous-based ancillary ligands was guided by a careful evaluation of their different electronic and steric properties. This evaluation aimed to understand how these ligands, once coordinated, could influence the structural, electronic, and catalytic activity of the corresponding complexes. The range of complexes showed moderate catalytic activity in the transfer hydrogenation of alcohols, with the best performing catalyst achieving 96 % conversion in 1 hour (TON=96, TOF=96 h⁻¹). All complexes were characterised using ¹H, ¹³C, ³¹P (where applicable) NMR spectroscopy, CHN (microanalysis) and HR-MS analyses. Single crystal structures were obtained for all nine new complexes, as well two new polymorphs of the precursor complex. Complimentary electrochemical (cyclic voltammetry) and density functional theory (DFT) studies provided additional insights into the structural and electronic properties of the different complexes.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 5","pages":""},"PeriodicalIF":2.2,"publicationDate":"2024-12-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143431550","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Front Cover: Molten Flux Synthesis of Plutonium (IV) Silicates K2PuSi2O7 and Rb2PuSi6O15 (Eur. J. Inorg. Chem. 36/2024)","authors":"Travis K. Deason,&nbsp;Gregory Morrison,&nbsp;Amir Mofrad,&nbsp;Jake Amoroso,&nbsp;David DiPrete,&nbsp;Theodore M. Besmann,&nbsp;Shanna L. Estes,&nbsp;Hans-Conrad zur Loye","doi":"10.1002/ejic.202483601","DOIUrl":"https://doi.org/10.1002/ejic.202483601","url":null,"abstract":"<p><b>The Front Cover</b> illustrates plutonium silicate crystals synthesized at Savannah River National Laboratory. The crystals were prepared by a flux growth method and represent a new crystal with Pu in its structure. These types of crystals are being investigated to better understand the immobilization of transuranic elements from nuclear waste. The Savannah River Site's F Area tank farm is in the background. More information can be found in the Research Article by H.-C. zur Loye and co-workers.\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"27 36","pages":""},"PeriodicalIF":2.2,"publicationDate":"2024-12-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202483601","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143187199","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Influence of the Halogen Anion Combination on the Spin Crossover Properties of Iron(II) Triazole Complexes","authors":"Arthur Sander,&nbsp;Maximilian Seydi Kilic,&nbsp;Jules Brehme,&nbsp;Kevin Tran,&nbsp;Christoph Wesemann,&nbsp;Prof. Franz Renz","doi":"10.1002/ejic.202400359","DOIUrl":"https://doi.org/10.1002/ejic.202400359","url":null,"abstract":"<p>In this paper we study a series of solid iron(II)-triazole spin crossover complexes of the formula [Fe(NH₂trz)₃]Br_2(x−1)Cl_2x, where the counterions bromide and chloride are present in the same structure in different ratios. Thus, the spin transition temperature also changes in the temperature range between the pure complexes [Fe(NH₂trz)₃]Br₂ and [Fe(NH₂trz)₃]Cl₂. Since these switching temperatures of the pure complexes are rather far apart, this allows us to examine how the SCO behavior of iron(II) triazole complexes with mixed counterions changes with different ratios. To achieve this, the complexes were synthesized with both counterions simultaneously using the salts FeBr₂ and FeCl₂ ⋅ 4 H₂O. The complexes were analyzed by IR and XRD measurements to confirm a successful synthesis. Energy dispersive X-ray spectroscopy (EDX) was further used to validate the results and to verify a homogeneous distribution of the mixed anions in all samples. This study reveals a linear switching behavior of the complexes depending on the substitution ratio with a temperature range between the homo ionic samples.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 5","pages":""},"PeriodicalIF":2.2,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202400359","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143431824","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Ag Nanoparticles-Modified FeVO4 Composite for Efficient Photocatalytic CO2 Reduction","authors":"Xinming Liang,&nbsp;Shan Hu,&nbsp;Fuhong Bi,&nbsp;Zixin Liu,&nbsp;Huilin Hu,&nbsp;Jinhua Ye,&nbsp;Defa Wang","doi":"10.1002/ejic.202400698","DOIUrl":"https://doi.org/10.1002/ejic.202400698","url":null,"abstract":"<p>Photoreduction of CO₂ and H₂O into fuels and value-added chemicals is an effective solution to address global energy issues. However, developing photocatalysts with high activity and selectivity remains a major challenge. Herein, we report Ag nanoparticles (NPs) loaded FeVO₄ (FVO) composite photocatalyst for highly efficient and selective photoreduction of CO₂ to CO. Under a 300 W Xe lamp irradiation, the optimal Ag₁-FVO catalyst exhibits a CO yield of 255.4 μmol g⁻¹ h⁻¹ and a CO selectivity of 99.7 %, which are dramatically higher than those of pure FVO alone. The significantly enhanced photocatalytic performance could be attributed to Ag NPs on the surface of FVO, which improve the separation efficiency of photogenerated carriers and promote the adsorption/activation of CO₂ molecules. This study suggests that modification of semiconductor photocatalysts with Ag NPs is an effective method for enhancing the CO₂ photoreduction activity.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 4","pages":""},"PeriodicalIF":2.2,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143118402","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Tailoring the Multi-Protolytic Equilibrium of Tin Porphyrins as Promising Molecular Catalyst for the Two-Electron Oxidation of Water in Artificial Photosynthesis","authors":"Reshma Joseph,&nbsp;Haritha Baby,&nbsp;Aswathy Kaiprampattuparambil Gopi,&nbsp;Shabna Kanjirathingal Ibrahim,&nbsp;Aparna Kallattil,&nbsp;Dr. Arun Thomas,&nbsp;Dr. Siby Mathew,&nbsp;Dr. Suja Haridas,&nbsp;Dr. Fazalurahman Kuttassery,&nbsp;Prof. Dr. Hiroshi Tachibana,&nbsp;Prof. Dr. Haruo Inoue,&nbsp;Dr. Sebastian Nybin Remello","doi":"10.1002/ejic.202400667","DOIUrl":"https://doi.org/10.1002/ejic.202400667","url":null,"abstract":"<p>Two-electron oxidation of water to form hydrogen peroxide is an alternative approach to overcome the photon-flux density problem as the bottleneck subject in artificial photosynthesis associated with molecular systems for photochemical water splitting. Tin-porphyrin complexes show promising activity and selectivity for the two-electron water-oxidation pathway. A key aspect of the reaction mechanism of these systems is the attack of OH⁻/H₂O to the activated axial oxygen atom as the reaction center of the one-electron oxidized species to form O−O bond, which is feasible when an odd electron is localized on axial oxygen. DFT calculations show that the spin of the odd electron is mostly localized on the axial oxygen atoms when they are in deprotonated states; hence, their pKa determine the applicability of these systems under the pH conditions adopted. The milder pH conditions are most preferable. To explore the conditions the effect of various porphyrin ring substituents on the pKa of the protonation–deprotonation process in A4 and A3B tin-porphyrin complexes have been studied here by spectrophotometric titration. Tetra-fluorophenyl (Sn−F4), tetra-chlorophenyl (Sn−Cl4), and tetra-methoxycarbonylphenyl (SnTCPPMester)-substituted Sn−A4 porphyrins have pKa1 values of 10.1 (Sn−F4), 9.8 (Sn−Cl4), and 6.7 (SnTCPPMester), which are in the increasing order of the electron-withdrawing effect, -F (σ_p=0.06)&lt;-Cl (0.23)&lt;-COOMe (0.45). For A3B (A=fluorophenyl or chlorophenyl, B=methoxycarbonylphenyl) Sn-porphyrins, pKa1 shifts to the smaller value (Sn−F3Mester: 9.4, Sn−Cl3Mester: 6.6), improving the pH range of the active species from basic to ambient pH. This study shows how the pH range of the active species can be effectively tailored by choosing the meso-substituents.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 4","pages":""},"PeriodicalIF":2.2,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143118401","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synthesis, Structure, Spectral and Electrochemical Properties of 5,6,7,9,10,11-Hexaaryl Substituted Meso-(p-Tolyl) 3-Pyrrolyl BODIPYs","authors":"Pinky Chauhan,&nbsp;Prof. Mangalampalli Ravikanth","doi":"10.1002/ejic.202400673","DOIUrl":"https://doi.org/10.1002/ejic.202400673","url":null,"abstract":"<p>Hexabrominated <i>meso</i>-(<i>p</i>-tolyl) 3-pyrrolyl BODIPY was regioselectively synthesized by treating <i>meso</i>-(<i>p</i>-tolyl) 3-pyrrolyl BODIPY with eight equivalents of Br₂ in CH₂Cl₂ under inert atmosphere at room temperature. Five different 5,6,7,9,10,11-hexaarylated <i>meso</i>-(<i>p</i>-tolyl) 3-pyrrolyl BODIPYs were synthesized by treating 5,6,7,9,10,11-hexabromo <i>meso</i>-(<i>p</i>-tolyl) 3-pyrrolyl BODIPY with various boronic acids under Suzuki coupling conditions. The X-ray structure obtained for hexabromo and hexaarylated 3-pyrrolyl BODIPYs showed slightly distorted structures. Absorption spectral studies revealed that the absorption bands in hexabromo and hexaarylated 3-pyrrolyl BODIPYs were bathochromically shifted compared to 3-pyrrolyl BODIPY. The hexabromo 3-pyrrolyl BODIPY was less fluorescent due to presence of heavy halogens whereas the hexaarylated 3-pyrrolyl BODIPYs emits moderately in the region of 687–736 nm with quantum yields in the range of 0.18–0.30 and singlet state lifetimes in 2.99–4.50 ns range. The electrochemical studies revealed that hexabrominated 3-pyrrolyl BODIPY undergo easier reduction compared to 3-pyrrolyl BODIPY. The hexaarylated 3-pyrrolyl BODIPYs showed one reversible/quasi-reversible oxidation and one reversible reduction and their redox behaviour depends on the type of electron donating or electron withdrawing substituents present at the pyrrole carbons. DFT/TD-DFT studies were in agreement with the experimental results. Group webpage: https://ravikanthlab.wixsite.com/mysite/</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 4","pages":""},"PeriodicalIF":2.2,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143118400","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Theoretical Insights into the Oxidation of Substrates by High-Spin Iron(III)-Acylperoxido Complexes","authors":"Gunasekaran Velmurugan,&nbsp;Peter Comba","doi":"10.1002/ejic.202400837","DOIUrl":"https://doi.org/10.1002/ejic.202400837","url":null,"abstract":"<p>While the oxidation of organic substrates by Fe^IV-oxido complexes has been studied extensively, there are only few highly reactive Fe^III-alkylperoxido complexes. We report here computational mechanistic work of a novel mononuclear nonheme Fe^III-phenylperoxido acetate complex, focusing on the splitting of the peroxide bond, the epoxidation of ethene and the hydroxylation of cyclohexane. Our results reveal that the peroxide bond undergoes homolysis, leading to the formation of an Fe^IV-oxido complex. Spectroscopic evidence supports the presence of an Fe^IV species, aligning with the observed product distribution. Additionally, we have explored a potential sigmatropic rearrangement mechanism. However, based on the activation barriers and initial product energy levels, the Fe^III rather than the Fe^V species is shown to be the active species in the initial step. For both, the epoxidation and hydroxylation reactions, stepwise mechanisms are proposed, involving the Fe^IV-oxido species as the catalytic intermediate. The energy barriers calculated for these pathways are significantly lower than those for concerted mechanisms, involving the Fe^III-peroxido species as direct oxidant. In particular, the calculated activation barrier in the Fe^IV-oxido pathway is 38 kJ/mol for the activation of the C=C bond in ethene, while the analogous step in the Fe^III-peroxido pathway is calculated to be as high as 183 kJ/mol. Our computational results indicate that the Fe^IV-oxido species is the active catalyst in these oxidation reactions.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 11","pages":""},"PeriodicalIF":2.2,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202400837","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143822130","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Organosilylated Cage Germoxanes Encapsulating Fluoride Ions for Creating Functional Nanomaterials","authors":"Taiki Hayashi,&nbsp;Kazuyuki Kuroda,&nbsp;Atsushi Shimojima","doi":"10.1002/ejic.202400614","DOIUrl":"https://doi.org/10.1002/ejic.202400614","url":null,"abstract":"<p>Recent advances in the design and synthesis of functionalized cage germoxanes that encapsulate fluoride ions to create various nanomaterials are presented. Organosilylation of the Ge−OH groups at the vertices of the cage is a versatile method for conferring solubility in organic solvents and chemical reactivity for grafting and cross-linking. Organosilylated cage germoxanes can be used to prepare nanoporous solids with tunable pore characteristics, self-healing silicone-based elastomers, and a new class of inorganic-organic hybrid ionic liquids. The unique properties of these nanomaterials arising from the Ge−O−Ge framework, fluoride anions encapsulated within the framework, counter cations outside the framework, and organosilyl groups at the vertices of the cage are described.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 2","pages":""},"PeriodicalIF":2.2,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143118399","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Spectroscopic Exploration Of Catalyst Dynamics And Electrochemical Properties Of Grubbs Second Generation In Different Solvent","authors":"O. Abiola Odewole,&nbsp;Martinus Rudi Swart,&nbsp;Elizabeth Erasmus","doi":"10.1002/ejic.202400356","DOIUrl":"https://doi.org/10.1002/ejic.202400356","url":null,"abstract":"<p>The phosphine (PCy₃) ligand dissociation equilibrium of the second generation Grubbs catalyst (<b>GII</b>) in different solvents (dichloromethane, dichloroethane, chloroform, tetrahydrofuran, and toluene) was determined to be pseudo first order with <i>k</i>_obs=0.8–2.6×10⁻⁴ s⁻¹. An electrochemically reversible behavior was observed for <b>GII</b> dissolved in the chlorinated solvents (DCM, DCE, and CLF). The formal reduction potentials, E°′, of <b>GII</b> in the different chlorinated solvents increased with increasing polarity index of the solvent. In THF, however, only oxidation of <b>GII</b> could be detected. Upon oxidation of <b>GII</b>, THF (with a lone pair electron on the oxygen), which is a highly coordinative solvent, nucleophilically attaches to the electrochemically generated Ru⋅⁺, resulting in a redox inactive THF-associated compound. A correlation was established between the ease of <b>GII</b> oxidation in the different solvents and the rate of PCy₃ dissociation in that solvent. The % yield of <b>GII</b>-catalyzed cross-metathesis product in the different solvents at 40 °C increases exponentially with increasing Gutmann donor number of the solvent increased, with DCM showing the highest yield. No metathesis could be detected in THF, consistent with the electrochemical data that THF coordinates to the positively charged or active <b>GII</b>, rending it inactive.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 5","pages":""},"PeriodicalIF":2.2,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202400356","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143431823","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}