Inorganic Chemistry最新文献_第2页

Pyruvic Acid Hydrogenation in Water by Diamine-Capped Ruthenium Nanoparticles. 二胺包覆钌纳米粒子在水中丙酮酸加氢的研究。

IF 4.3 2区化学

Inorganic Chemistry Pub Date : 2025-07-03 DOI: 10.1021/acs.inorgchem.5c01656

Werner Oberhauser, Lorenzo Poggini, Laura Capozzoli, Maria V Pagliaro, Serena Coiai, Claudio Evangelisti

{"title":"Pyruvic Acid Hydrogenation in Water by Diamine-Capped Ruthenium Nanoparticles.","authors":"Werner Oberhauser, Lorenzo Poggini, Laura Capozzoli, Maria V Pagliaro, Serena Coiai, Claudio Evangelisti","doi":"10.1021/acs.inorgchem.5c01656","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c01656","url":null,"abstract":"Small-sized (dm = 2.07 nm) diamine (L)-stabilized ruthenium nanoparticles (NPs) were successfully synthesized upon the reaction of Ru(acetylacetonate)3 with hydrogen in the presence of L and dichloromethane. The obtained L-capped ruthenium nanoparticles (RuL) were used as-synthesized and after deposition on the surface of carbon (CK), featured by a high surface area (RuL@CK, Ru content of 0.44 wt %) to selectively catalyze the hydrogenation of pyruvic acid in water at reaction temperatures up to 80 °C. The high efficiency of the latter catalyst emerged from parallel catalytic reactions conducted with the reference catalyst Ru@CK, which was obtained by applying the same synthesis protocol in the absence of L. The role of L in the catalytic pyruvic acid hydrogenation reactions emerged from catalytic reactions combined with high-resolution transmission electron microscopic, X-ray photoelectron spectroscopic, and electrochemical studies.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":" ","pages":""},"PeriodicalIF":4.3,"publicationDate":"2025-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144558416","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

Computational Investigations of Metal-Metal Bonding in Molecular Thorium Compounds and Ce and Group IV Analogues. 分子钍化合物、Ce和IV族类似物中金属-金属键的计算研究。

IF 4.3 2区化学

Inorganic Chemistry Pub Date : 2025-07-03 DOI: 10.1021/acs.inorgchem.5c01812

Josef Tomeček, Stephen T Liddle, Nikolas Kaltsoyannis

{"title":"Computational Investigations of Metal-Metal Bonding in Molecular Thorium Compounds and Ce and Group IV Analogues.","authors":"Josef Tomeček, Stephen T Liddle, Nikolas Kaltsoyannis","doi":"10.1021/acs.inorgchem.5c01812","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c01812","url":null,"abstract":"We report quantum chemical investigations of metal-metal bonding in molecular thorium clusters and compare them with cerium and group IV transition metal analogues. We explore periodic trends in metal-metal bonding and the roles of electron delocalization, orbital diffuseness, and oxidation state. As cluster size increases in the series [{Th(η8-COT)Cl2}nK2] (COT = C8H8, n = 2-5, 2-5) and [Th4Cl4(η8-COT)4]2+ (T), n-center-2-electron bonding weakens. Quantum theory of atoms in molecules (QTAIM) analysis finds Th-Th bond paths only in 2 and 3, while T exhibits a non-nuclear attractor, indicating charge concentration in the [Th4Cl4]10+ core. In the Ce analogues, Ce-Ce bonding is observed only in oxidation states below +3. Calculations on [Ce3Cl6]z (z = 1-3) and Cp-stabilized analogues show Ce-Ce bond shortening with increasing population of the 3-center MOs. The QTAIM confirms Ce-Ce bond paths in [Ce3Cl6]+, [Ce3Cl6(η5-Cp)3]-, and [Ce3Cl6(η5-Cp)3K2]. Group IV analogues reveal variations in metal-metal bonding on progressing from the contracted 3d AOs of Ti to the more diffuse 6d AOs of Rf. In [M3Cl6(η8-COT)3K2] (3-M), only 3-Rf exhibits QTAIM bond paths similar to the Th analogue, suggesting that only the 6d orbitals are sufficiently diffuse as to support such interactions.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":" ","pages":""},"PeriodicalIF":4.3,"publicationDate":"2025-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144558410","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

State Crossing Affects Photolysis Efficiency of Iron(III) Aqua Hydroxo Complexes. 状态交叉影响铁（III）水羟基配合物的光解效率。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-07-02 DOI: 10.1021/acs.inorgchem.5c01646

Hao Cen,Jingpei Huo,Jun Cao

{"title":"State Crossing Affects Photolysis Efficiency of Iron(III) Aqua Hydroxo Complexes.","authors":"Hao Cen,Jingpei Huo,Jun Cao","doi":"10.1021/acs.inorgchem.5c01646","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c01646","url":null,"abstract":"The iron(III)-(hydro)oxides and hydrated iron(III) ion respond to important applications in many fields, but their ligand-to-metal charge-transfer (LMCT) reactions receive less attention due to short excited-state lifetime or degradation. Here, we apply the ab initio multireference method to investigate the charge transfer photolysis of iron(III) aqua hydroxo complexes. Our studies reveal that both Fe-OH2 bond photolysis and photohydrolysis can occur simultaneously in iron(III) aqua complexes, with the second hydration shell promoting photohydrolysis by serving as a proton acceptor. During the photolysis of the Fe-OH2 bond, the reactive sextet electronic states can additionally undergo intersystem crossing transitions to lower-energy, nonreactive quartet states, which further reduces the overall photolytic efficiency of iron(III) aqua complexes. In iron(III)-hydroxy complexes, direct photolysis of the Fe-OH bond is the predominant pathway. In dimeric iron(III) complexes, lower LMCT states would undergo internal conversion to reach the ground state during photolysis of the bridging Fe-OH/Fe-O bond, leading to a low excited-state reactivity. Our theoretical results provide an improved understanding of the iron-oxygen bond photolysis of iron(III) aqua hydroxo complexes and complement previous explanations to experimental observations. These results are also potentially helpful for understanding the surface photochemistry of iron oxides in aqueous solutions and LMCT-triggered water oxidation.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"45 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144547752","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

Cluster Expansion of Luminescent Digold(I) and Disilver(I) Phosphine-Phosphide Oxide Complexes. 发光二金(I)和二银(I)磷化氢-磷化物氧化物配合物的团簇扩展。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-07-02 DOI: 10.1021/acs.inorgchem.5c01816

Mariia Beliaeva,Andrey Belyaev,Andreas Steffen,Igor O Koshevoy

{"title":"Cluster Expansion of Luminescent Digold(I) and Disilver(I) Phosphine-Phosphide Oxide Complexes.","authors":"Mariia Beliaeva,Andrey Belyaev,Andreas Steffen,Igor O Koshevoy","doi":"10.1021/acs.inorgchem.5c01816","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c01816","url":null,"abstract":"Deprotonation of a diphosphine-secondary phosphine oxide ligand (o-Ph2PC6H4)2P(O)H (HP3O) affords disilver(I) and digold(I) complexes [M2(P3O)2], M = Ag (1) and Au (2). These compounds readily add coordinatively unsaturated AuX fragments (X = C6F5, SPh) by means of metallophilic interactions supported by bridging ligands. The extension of the metal core produces a series of penta- to octanuclear clusters [{M2(P3O)2}(AuX)n] 3-7 (n = 3-6), the structures of which depend on the X group, the nature of the constituting metals, and P = O···HR hydrogen bonding. The newly synthesized clusters demonstrate moderate to intense luminescence as microcrystalline powders, predominantly originating from the triplet excited state and covering a range of wavelengths from 517 to 585 nm. Complexes 3-5 containing perfluorophenyl ligands exhibit high photoemission quantum yields under ambient conditions of up to 0.76 in combination with a relatively short lifetime of 0.98 μs for the pentagold cluster [Au2(P3O)2(AuC6F5)3] (4). The results illustrate a feasible approach for the preparation of nonionic d10 coinage metal bright luminophores, derived from a hybrid P{OP-}P scaffold.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"27 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144547753","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 Luminescent Zirconium-Pentacarboxylate Framework with 10-Connected Zr6 Clusters for Dichromate Detection. 具有10连接Zr6簇的发光锆-五羧酸盐框架用于重铬酸盐检测。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-07-02 DOI: 10.1021/acs.inorgchem.5c02368

Zhen-Sha Ma,Jun Xia,Shuai Chang,Kang Zhou,Xiao-Yuan Liu

引用次数: 0

Scandium─Group 13 Heterobimetallic Methylidene Clusters. 钪─13族杂双金属亚甲基团簇。

IF 4.3 2区化学

Inorganic Chemistry Pub Date : 2025-07-02 DOI: 10.1021/acs.inorgchem.5c01520

Gernot T L Zug, Cäcilia Maichle-Mössmer, Reiner Anwander

{"title":"Scandium─Group 13 Heterobimetallic Methylidene Clusters.","authors":"Gernot T L Zug, Cäcilia Maichle-Mössmer, Reiner Anwander","doi":"10.1021/acs.inorgchem.5c01520","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c01520","url":null,"abstract":"A straightforward synthesis of Cp*2Sc(AlMe4) (Cp* = C5Me5) applying Cp*2ScCl(thf) and LiAlMe4/AlMe3 is described. Donor-assisted trimethyltriel exchange gives access to Cp*2Sc(EMe4) (E = Ga, In), which represent the first scandium tetramethylgallate and tetramethylindate complexes. Thermal treatment of Cp*2Sc(EMe4) (E = Ga, In) in benzene leads to the isolation of methylidene clusters Cp*6Sc4E8(CH2)12Me6 (E = Ga, In). This methyl group deprotonation differs from the benzene activation previously observed for Cp*2Y(EMe4) (E = Al, Ga). Treatment of Cp*2Sc(EMe4) (E = Al, Ga) with excess GaMe3 in benzene at elevated temperatures generated Ga8(CH2)12, following the known reactivities of Cp*2Ln(GaMe4) (Ln = Y, Lu) with GaMe3. Analogous reactions of scandocene complexes Cp*2Sc(EMe4) (E = Al, In) with excess InMe3 at elevated temperatures did not yield the putative homoleptic indium methylidene. Instead, the methylidene cluster Cp*4Sc4In8(CH2)12Me8 was isolated, which features half-sandwich scandium fragments exclusively. A reaction of InMe3 and HCp* at high temperatures yielded Me2InCp*InMe3, which might incorporate the missing Cp* ligands in the cluster formations. Rare-earth-metal compounds were analyzed by SC-XRD, ICP-OES and elemental analysis. Compounds Cp*2Sc(EMe4) (E = Ga, In) and [Cp*2Sc(ClAlMe3)]2 were additionally analyzed by 1H, 13C{1H}, 45Sc NMR as well as 1H and 45Sc variable temperature NMR studies.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":" ","pages":""},"PeriodicalIF":4.3,"publicationDate":"2025-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144551437","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

Halogen Substituents Regulate the Types of Reactive Oxygen Species Generated by Ca(II)-Based Luminescent HOFs, and Their Smart Sensing and Photodynamic Sterilization. 卤素取代基调控Ca（II）基发光HOFs生成的活性氧类型及其智能传感和光动力灭菌。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-07-02 DOI: 10.1021/acs.inorgchem.5c02495

Xin-Yi Huang,Guan-Huang Zhang,Zhi-Rong Luo,Fupei Liang,Zhong-Hong Zhu,Hua-Hong Zou

{"title":"Halogen Substituents Regulate the Types of Reactive Oxygen Species Generated by Ca(II)-Based Luminescent HOFs, and Their Smart Sensing and Photodynamic Sterilization.","authors":"Xin-Yi Huang,Guan-Huang Zhang,Zhi-Rong Luo,Fupei Liang,Zhong-Hong Zhu,Hua-Hong Zou","doi":"10.1021/acs.inorgchem.5c02495","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c02495","url":null,"abstract":"Hydrogen-bonded organic frameworks (HOFs) have demonstrated unique application advantages in fields such as ion sensing and photodynamic sterilization. Herein, four HOFs were obtained by using 8-hydroxyquinoline with different heavy atom substituents to react with Ca(NO3)2·4H2O. Ca-HOFs all have excellent smart sensing performance behavior to SO42- ions, and their detection limits are 3.45, 2.15, 2.29, and 1.34 μM, respectively. In addition, Ca-HOF-1/3/4 also exhibits highly sensitive sensing performance behavior to Cr2O72- ions, and their detection limits are 0.833, 1.72, and 1.11 μM, respectively. Notably, light-driven switching of reactive oxygen species (ROS) in Ca-HOFs can be easily achieved by regulating the heavy atom substituents on the ligands. Ca-HOF-1 and Ca-HOF-2 containing -Cl substitution only efficiently produce type II ROS-1O2 under light irradiation conditions, while Ca-HOF-3 and Ca-HOF-4 containing -Br or -I substitution only produce type I ROS-•OH under light irradiation conditions. To the best of our knowledge, this is the first time that the generation of different types of ROS in HOF photosensitizers under light irradiation conditions has been regulated by changing the halogen-heavy atom substituents. This work not only opens a door for regulating the generation of specific ROS by photosensitizers but also promotes the development of efficient HOF-based photosensitizers.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"29 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144547790","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

Unveiling the Role of Ligand Assistance in H2 Activation and CO2 Hydrogenation Catalyzed by an Iridium Complex: A DFT Study. 揭示配体辅助在铱配合物催化H2活化和CO2加氢中的作用：DFT研究。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-07-02 DOI: 10.1021/acs.inorgchem.5c01506

Qiping Zhu,Zuzeng Qin,Fenglai Lu,Dianpeng Li

{"title":"Unveiling the Role of Ligand Assistance in H2 Activation and CO2 Hydrogenation Catalyzed by an Iridium Complex: A DFT Study.","authors":"Qiping Zhu,Zuzeng Qin,Fenglai Lu,Dianpeng Li","doi":"10.1021/acs.inorgchem.5c01506","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c01506","url":null,"abstract":"Density functional theory (DFT) calculations were employed to elucidate the mechanistic pathways of hydrogen activation and CO2 addition mediated by a novel iridium catalyst. The results demonstrate that hydrogen activation proceeds efficiently via an oxidative addition mechanism at the Ir(I) center, followed by ligand-assisted heterolysis. Detailed distortion-interaction and energy decomposition analyses indicate that the oxidative addition at the Ir(I) center exhibits stronger orbital interactions, which are key determinants of the selectivity in hydrogen activation. In the CO2 addition reaction, the trihydride complex reacts with DBU, inducing a redox transition from Ir(III) to an Ir(I) dihydride intermediate, which undergoes ligand-assisted stepwise hydride transfer. This dynamic reduction pathway significantly lowers the reaction barrier and facilitates hydride transfer. Compared to the direct hydrogenation pathway involving Ir(III) species, this route exhibits a substantially lower energy barrier. Energy decomposition and noncovalent interaction analyses further reveal that the reduced Pauli repulsion in the Ir(I)-centered pathway is a critical factor contributing to its lower activation energy and higher selectivity. These findings highlight the significance of the Ir(I)/Ir(III) dynamic redox transition in catalytic processes, providing valuable theoretical insights for the development of efficient catalysts for hydrogen activation and CO2 conversion.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"6 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144533433","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

Polarization of a Rotationally Degenerate Pair of Bands Causing the Uniaxial Magnetism of Permanent Magnets. 引起永磁体单轴磁性的旋转简并带对极化。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-07-02 DOI: 10.1021/acs.inorgchem.5c01135

Changhoon Lee,Taesu Park,Hyun-Joo Koo,Jae-Hoon Park,Ji Hoon Shim,Myung-Hwan Whangbo

{"title":"Polarization of a Rotationally Degenerate Pair of Bands Causing the Uniaxial Magnetism of Permanent Magnets.","authors":"Changhoon Lee,Taesu Park,Hyun-Joo Koo,Jae-Hoon Park,Ji Hoon Shim,Myung-Hwan Whangbo","doi":"10.1021/acs.inorgchem.5c01135","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c01135","url":null,"abstract":"By analogy with the selection rule governing the uniaxial magnetism of magnetic insulators, we found that the uniaxial magnetism of permanent magnets (i.e., itinerant or metallic ferromagnets) requires the presence of a strong polarization (i.e., unequal populations of the two members constituting a pair) in one of the three rotationally degenerate pairs, (xz2, yz2), [xyz, (x2 - y2)z], and [x(x2 - 3y2), y(y2 - 3x2)], of the f-bands in rare-earth (RE)-based ones, and in one of the two rotationally degenerate pairs, (xz, yz) and (xy, x2 - y2), of the d-bands in RE-free ones. This requirement was confirmed by determining the magnetocrystalline anisotropy energies (MAEs) of permanent magnets SmCo5 and MnAl as well as the partial density of states (PDOS) plots of their rotationally degenerate pairs of bands on the basis of density functional theory (DFT) calculations. As a quantitative measure for the strength of the pair-polarization in each rotationally degenerate pair of bands, we defined the pair-polarization index Δp, which is associated with the calculated PDOS plots. Finally, we presented qualitative arguments with which to explain why a strong pair-polarization occurs in a particular rotationally degenerate pair in both RE-based and RE-free permanent magnets.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"13 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144533435","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

Sc3+-Promoted Selective Oxygenation of Olefins with H2O2 by a Ligand-Free Iron Catalyst: Insights into the Nature of Active Oxidant. 无配体铁催化剂催化Sc3+促进烯烃与H2O2选择性氧化：对活性氧化剂性质的认识。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-07-02 DOI: 10.1021/acs.inorgchem.5c02224

Sabyasachi Mahapatra,Rahul Dev Jana,Satadal Paul,Tapan Kanti Paine

{"title":"Sc3+-Promoted Selective Oxygenation of Olefins with H2O2 by a Ligand-Free Iron Catalyst: Insights into the Nature of Active Oxidant.","authors":"Sabyasachi Mahapatra,Rahul Dev Jana,Satadal Paul,Tapan Kanti Paine","doi":"10.1021/acs.inorgchem.5c02224","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c02224","url":null,"abstract":"Developing catalytic methods for the selective oxygenation of olefins remains an important objective in oxidation chemistry. Many iron-based catalysts have been reported in that pursuit. However, most catalytic systems rely on supporting ligands and often display nonselective oxidation via free radical pathways. Herein, we report a catalytic system combining a simple iron salt and Lewis acid (Sc(OTf)3) in acetonitrile for the selective epoxidation of a series of olefins with hydrogen peroxide. An iron(II)-scandium(III) triflate complex, formed in the reaction mixture, activates hydrogen peroxide, leading to a metal-based oxidant and not any radical species, thereby suggesting a mechanism different from the Fenton chemistry. An electrophilic oxidant is involved in the Sc3+-promoted epoxidation reactions. Quantum chemical analysis reveals the identity of the active oxidant responsible for the epoxidation reaction and elucidates the role of Sc3+ ions in the mechanistic pathway. The proximity of Sc(OTf)3 to the iron center helps in the O-O bond cleavage and generates the active oxidant required for the epoxidation reaction. This work demonstrates that the catalytic activity of simple iron salts in combination with Sc(OTf)3 in acetonitrile without the requirement of any supporting ligand does not involve free radicals, while affecting the selective oxygenation of olefins.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"648 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144533437","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