Inorganic Chemistry最新文献_第8页

Quantifying Base-Dependent Lewis Acidity in Substituted Boranes through DFT and Machine Learning 通过DFT和机器学习量化取代硼烷中碱依赖的刘易斯酸度

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-10-19 DOI: 10.1021/acs.inorgchem.6c04676

Amir Mahdian,Kari Laasonen,Kaveh Farshadfar

{"title":"Quantifying Base-Dependent Lewis Acidity in Substituted Boranes through DFT and Machine Learning","authors":"Amir Mahdian,Kari Laasonen,Kaveh Farshadfar","doi":"10.1021/acs.inorgchem.6c04676","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c04676","url":null,"abstract":"The dependence of Lewis acidity on the interacting base is established. Here, density functional theory calculations and machine-learning analysis quantify substituent effects and base dependence within a combinatorial library of 816 trisubstituted boranes constructed from 16 substituents. Interactions with five probe bases (H2O, NH3, C5H5N, PMe3, and Cl–) yield 3927 calculated adduct formation free energies in dichloromethane. Electron-withdrawing substituents generally enhance borane Lewis acidity, whereas electron-donating substituents attenuate it. The magnitude of these effects varies with the base, producing changes and occasional reversals in relative acidity rankings. PMe3 shows the strongest dependence on substituent identity among the investigated bases. Weak linear correlations between isolated-borane global hardness and adduct formation free energy indicate limited predictive power for this single descriptor. Random forest models describe the computed trends, while SHAP analysis identifies the summed Hammett σp parameter, the borane–base frontier orbital energy gap, and borane electrophilicity as the most influential descriptors in the model. These results provide a quantitative map of substituent effects and the transferability of relative borane acidity rankings across the investigated bases.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"11 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149210890","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

Bicarbonate Liquid Condensate Controls Manganese Partitioning in Calcite 碳酸氢钠液体冷凝水控制方解石中锰的分馏

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-10-19 Epub Date: 2026-10-06 DOI: 10.1021/acs.inorgchem.6c02302

Ayumi Koishi, Chaya Weeraratna, Musahid Ahmed, Chenhui Zhu, Wenming Dong, Karen C. Bustillo, Colin Ophus, Piotr Zarzycki, Laura N. Lammers, Michael L. Whittaker

{"title":"Bicarbonate Liquid Condensate Controls Manganese Partitioning in Calcite","authors":"Ayumi Koishi, Chaya Weeraratna, Musahid Ahmed, Chenhui Zhu, Wenming Dong, Karen C. Bustillo, Colin Ophus, Piotr Zarzycki, Laura N. Lammers, Michael L. Whittaker","doi":"10.1021/acs.inorgchem.6c02302","DOIUrl":"10.1021/acs.inorgchem.6c02302","url":null,"abstract":"Crystals formed in aqueous solutions often encode chemicalmemoriesof their growth environment. However, the molecular pathway of elementpartitioning that links solution chemistry to solid composition remainselusive when growth proceeds through nonclassical intermediates. Inthis study, we investigated calcite growth mechanisms in the presenceof aqueous manganese (Mn2+) under chemostat conditionsusing a custom titration method. At near-neutral pH, where bicarbonateions dominate, we show that Mn2+ triggers the formationof bicarbonate-rich, ion-paired liquid condensates that accumulateat the calcite–water interface and control Mn incorporationinto the solid phase. Time-resolved in situ X-ray scattering and Ramanspectroscopy, combined with cryogenic transmission electron microscopyand molecular dynamics simulations, reveal a pathway in which thesecondensates deprotonate and dehydrate into Mn-bearing amorphous carbonatethat crystallizes into polycrystalline calcite–rhodochrositeinterfacial solid solutions with progressively increasing Mn content.These results identify an interfacial, bicarbonate-rich liquid condensateas a mechanistic link between crystallization pathway and elementpartitioning, suggesting that nanoscale interfacial fluid organizationcan dominate selective ion uptake during crystallization in multicomponentaqueous environments that are relevant to geoscience, environmentalscience, chemistry, or materials science.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"65 41","pages":"24116–24128"},"PeriodicalIF":4.6,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149091940","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

Tetranuclear Copper Cluster of N2O Reductase: A Distinctive Copper–Sulfur Metallocluster N2O还原酶的四核铜簇：一种独特的铜硫金属簇

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-10-19 Epub Date: 2026-10-06 DOI: 10.1021/acs.inorgchem.6c04238

Sofia R. Pauleta, José J. G. Moura, Isabel Moura

{"title":"Tetranuclear Copper Cluster of N2O Reductase: A Distinctive Copper–Sulfur Metallocluster","authors":"Sofia R. Pauleta, José J. G. Moura, Isabel Moura","doi":"10.1021/acs.inorgchem.6c04238","DOIUrl":"10.1021/acs.inorgchem.6c04238","url":null,"abstract":"Copper is an essentialelement involved in several cofactorsandorganometallic compounds used as catalysts. Although most biologicalcopper centers contain one to three copper ions, nature has evolveda unique tetranuclear copper–sulfur cluster that has attractedthe attention of both biochemists and inorganic chemists. This multinuclearcopper center has only been observed in one enzyme, nitrous oxidereductase, which catalyzes the reduction of nitrous oxide to dinitrogen,the final step of the denitrification pathway. The structural, spectroscopic,and kinetic properties of this [4CuS] cluster have been the subjectof extensive investigation, revealing that it exists in two distinctforms within the enzyme, CuZ[4Cu:2S] and CuZ*[4Cu:1S], with differentoxidation states, spectroscopic signatures, and catalytic properties.These features are discussed together with recent advances in understandingthe biosynthesis and assembly of this cluster. Inorganic chemistshave synthesized a variety of structural and functional models ofthe CuZ cluster, although none fully reproduces the electronic structureand catalytic efficiency of the native active center. This reviewdiscusses the interplay between biological and synthetic studies,illustrating how advances in one field continue to inspire progressin the other while identifying the challenges that must be overcometo achieve truly functional biomimetic catalysts.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"65 41","pages":"24083–24096"},"PeriodicalIF":4.6,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149092057","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

Comprehensive Study of Early Transition Metal–Ammonia Solvated Electron Precursors with a Methyl Ligand: The Role of Metal–Carbon Bond in Diffuse Orbitals, Excited States, and Stability 含甲基配体的早期过渡金属-氨酰化电子前体的综合研究：金属-碳键在扩散轨道、激发态和稳定性中的作用

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-10-19 Epub Date: 2026-10-07 DOI: 10.1021/acs.inorgchem.6c04522

Andrei Evdokimov, Evangelos Miliordos

{"title":"Comprehensive Study of Early Transition Metal–Ammonia Solvated Electron Precursors with a Methyl Ligand: The Role of Metal–Carbon Bond in Diffuse Orbitals, Excited States, and Stability","authors":"Andrei Evdokimov, Evangelos Miliordos","doi":"10.1021/acs.inorgchem.6c04522","DOIUrl":"10.1021/acs.inorgchem.6c04522","url":null,"abstract":"Solvated electronprecursors (SEPs) are coordinationcomplexesthat accommodate one or more electrons in diffuse, hydrogenic-typeorbitals at the periphery of the molecular skeleton. Prototypicalmetal–ammonia complexes, observed in both gas and condensedphases, serve as building units for a novel class of electrides. AnchoringSEPs to inert surfaces (surface-immobilized SEP electrides, SISEPEs)offers materials suited for redox catalysis and quantum computinghardware. The titled (NH3)5MCH3 speciesserve as a model for the active sites of SISEPEs. To characterizetheir electronic structure and stability, high-level wavefunctionand density functional theory calculations are performed for M = Sc,Ti, V, and Cr. Beyond the valence 3d electrons, thesecomplexes host one electron in hydrogenic-type diffuse peripheralorbitals, with low-lying electronic states populating the 1s, 1p,1d, and 2s outer diffuse orbitals. Compared to the corresponding purehexacoordinated metal–ammonia complexes, (NH3)5MCH3 disfavors migration of an ammonia ligand tothe second solvation shell, and the diffuse electron density is polarizedaway from the methyl ligand. These findings provide a theoreticalframework for designing and characterizing SISEPE materials and highlightthe role of the M-C bond in modulating stability, electronic excitationpatterns, and the spatial characteristics of the outer diffuse orbitals.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"65 41","pages":"24593–24602"},"PeriodicalIF":4.6,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151458","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

Phase Behavior and Solid-State Photoreactivity of Organometallic Ionic Plastic Crystals with Cyanoborate Anions 含氰硼酸盐阴离子的有机金属离子塑料晶体的相行为和固态光反应性

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-10-19 Epub Date: 2026-10-05 DOI: 10.1021/acs.inorgchem.6c04353

Ryota Inoue, Haruka Koshino, Yasuhide Iwamoto, Kenta Hongo, Tomoyuki Mochida

{"title":"Phase Behavior and Solid-State Photoreactivity of Organometallic Ionic Plastic Crystals with Cyanoborate Anions","authors":"Ryota Inoue, Haruka Koshino, Yasuhide Iwamoto, Kenta Hongo, Tomoyuki Mochida","doi":"10.1021/acs.inorgchem.6c04353","DOIUrl":"10.1021/acs.inorgchem.6c04353","url":null,"abstract":"Ionicplastic crystals (IPCs) exhibit long-range translationalorder with orientational disorder and enhanced molecular mobility,yet their chemical reactivity remains unexplored. Salts of the sandwich-typeRu complex cation [Ru(Cp)(C6H6)]+ ([1]+) often exhibit IPC phases, while cyanoboratesalts of [1]+ undergo photochemical reactionsto form polynuclear complexes in solution and in the ionic-liquidstate. These properties prompted us to synthesize [1]BE(CN)3 (E = F, H, or Me) and [1]BE2(CN)2 (E = F or Et) and investigate their phase behavior and photoreactivityin IPC phases. All five salts exhibited IPC phases, with transitiontemperatures from the low-temperature crystalline phase to the IPCphase ranging from 277 to 378 K; three underwent the transition below300 K. UV irradiation of these three salts in their IPC phases affordedcubane-type tetranuclear complexes from [1]BF(CN)3 and [1]BH(CN)3 with conversions of50–77%, whereas [1]BF2(CN)2 gave an anionic dinuclear complex along with decomposition products.In contrast, irradiation of [1]BH(CN)3 and[1]BMe(CN)3 in their low-temperature crystallinephases gave conversions of only 18% and 11%, respectively. These resultsdemonstrate that the high molecular mobility of IPCs enables solid-statephotochemistry, with the salts acting as both reactants and reactionmedia.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"65 41","pages":"24548–24555"},"PeriodicalIF":4.6,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149091538","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 Sterically Encumbered Triarylborane Enabling CO2 Reduction to Formate by Electrons and Protons 一种能使CO2通过电子和质子还原生成甲酸的立体负载三芳基硼烷

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-10-19 Epub Date: 2026-10-03 DOI: 10.1021/acs.inorgchem.6c03816

Felix Meyer, Ludwig Zapf, Eric Rivard, Inke Siewert

{"title":"A Sterically Encumbered Triarylborane Enabling CO2 Reduction to Formate by Electrons and Protons","authors":"Felix Meyer, Ludwig Zapf, Eric Rivard, Inke Siewert","doi":"10.1021/acs.inorgchem.6c03816","DOIUrl":"10.1021/acs.inorgchem.6c03816","url":null,"abstract":"Borohydrides are widely used sources of hydride ions(H–), but their conventional synthesis from highlyreducing metal hydridesis energetically demanding and undermines sustainable applications.Herein, we report a sterically encumbered thioether-substituted triarylborane, 1,2-(tBuS)C6H4(BMes2) (3) (Mes = 2,4,6-Me3C6H2), which is highly air- and moisture-stable. 3 exhibits a one-electron reduction at E0 = −2.62 V vs Fc+|0 and a radical anionhalf-lifetime of ∼0.5 s in THF, enabling bimolecular follow-upreactivity. Indeed, two-electron reduction and protonation of 3 with KC8/[DBUH]+ (DBU = 1,8-diazabicyclo[5.4.0]undec-7-ene)or hydride transfer from Li(AlH4) affords the borohydride 4–. From a hydricity–potentialcorrelation, we estimate a hydricity of ∼36 kcal mol–1 in MeCN, which allows 4– to reduce H+ to H2 and CO2 to formateunder ambient conditions in almost quantitative yields. The reactionof 3, [DBUH]+, KC8, and CO2 furnishes potassium formate in ∼90% spectroscopicyield, establishing a closed synthetic cycle for CO2 reductionby protons and electrons at a boron center. These results highlighthow tailor-made, redox-active boranes can complement transition-metalhydrides as modular, metal-free platforms for coupling renewable electronsand protons in CO2 utilization chemistry.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"65 41","pages":"24410–24417"},"PeriodicalIF":4.6,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149091540","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

Lanthanide Contraction Associated Coordination Regimes and Photocatalytic Performance of Polyoxometalate-Based Lanthanide Phosphonates 基于多金属氧酸盐的镧系磷酸盐收缩相关配位体系和光催化性能

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-10-19 Epub Date: 2026-10-01 DOI: 10.1021/acs.inorgchem.6c03579

Lin-Lin Wang, Hong-Li Jia, Jian-Jie Xu, Qi-Ming Qiu, Chuan-Bing Hou, Wei Li, Hong-Liang Han, Heng-Yun Ye, Rui-Lin Yang, Qiong-Hua Jin

{"title":"Lanthanide Contraction Associated Coordination Regimes and Photocatalytic Performance of Polyoxometalate-Based Lanthanide Phosphonates","authors":"Lin-Lin Wang, Hong-Li Jia, Jian-Jie Xu, Qi-Ming Qiu, Chuan-Bing Hou, Wei Li, Hong-Liang Han, Heng-Yun Ye, Rui-Lin Yang, Qiong-Hua Jin","doi":"10.1021/acs.inorgchem.6c03579","DOIUrl":"10.1021/acs.inorgchem.6c03579","url":null,"abstract":"Lanthanide contraction provides a continuous scale fortuning coordinationstructures, yet its systematic use in photoactive materials remainsunderexplored. Herein, 14 POM-phosphonate-lanthanide hybrids fromLa to Lu (excluding Pm) were synthesized under mild conditions. Single-crystalXRD identifies three coordination regimes: La3+ at theeight/nine-coordination boundary, Ce3+-Yb3+ adoptingstable eight-coordination, and Lu3+ undergoing a ligand-deficienttransition due to steric congestion. The Sm3+ complex 5b, obtained under diffusion conditions, exhibits the samemotif as Lu3+ complex, indicating that crystal growth conditionscan influence coordination-mode selection. Combined with band-structureanalysis, EIS, radical trapping, EPR, and HPLC-MS, the photocatalyticmechanism was investigated. This work converts lanthanide contractionfrom a descriptive concept into an experimental framework for constructingstructure-performance correlations.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"65 41","pages":"24319–24330"},"PeriodicalIF":4.6,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149091599","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}

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Linker Chlorination Enhances Xe Adsorption and Xe/Kr Separation in Metal–Organic Frameworks 氯化接合剂增强金属-有机骨架中Xe吸附和Xe/ k分离

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-10-19 Epub Date: 2026-10-06 DOI: 10.1021/acs.inorgchem.6c04424

Hui-Fang Ma, Yu-Ling Wang, Junmin Chen, Hui-Ping Xiao, Wen-Rou Yu, Qing-Yan Liu

引用次数: 0

Porphyrin-Based Lanthanide Metal–Organic Layers Amplify the Reactive Oxygen Species Storm for Photodynamic Therapy, and Photoresponsive Radioactive UO22+ Ions 卟啉基镧系金属-有机层样品：用于光动力治疗的活性氧风暴和光响应性放射性UO22+离子

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-10-19 Epub Date: 2026-10-05 DOI: 10.1021/acs.inorgchem.6c04244

Yuan-Ju Zhang, Guan-Huang Zhang, Yu-Feng Wang, Hua-Hong Zou, Fu-Pei Liang, Zhong-Hong Zhu, Hai-Ling Wang

{"title":"Porphyrin-Based Lanthanide Metal–Organic Layers Amplify the Reactive Oxygen Species Storm for Photodynamic Therapy, and Photoresponsive Radioactive UO22+ Ions","authors":"Yuan-Ju Zhang, Guan-Huang Zhang, Yu-Feng Wang, Hua-Hong Zou, Fu-Pei Liang, Zhong-Hong Zhu, Hai-Ling Wang","doi":"10.1021/acs.inorgchem.6c04244","DOIUrl":"10.1021/acs.inorgchem.6c04244","url":null,"abstract":"Porphyrinderivatives employed for photodynamic therapy(PDT) readilyundergo intense π–π stacking, triggering drasticquenching of fluorescence and reactive oxygen species (ROS), whichseverely restricts their practical utilization in PDT research. Inthis work, meso-tetrakis(4-carboxyphenyl)porphyrin (TCPP) was adoptedas an organic linker to coordinate with binuclear Eu(III)-complexsecondary building units (SBUs), affording a two-dimensional metal–organiclayer (Eu-TCPP) capable of generating light-triggeredmassive ROS bursts. Combined electron paramagnetic resonance (EPR)characterizations and targeted fluorescent probes collectively validatethat Eu-TCPP is able to simultaneously produce abundanttype I and type II ROS cascades upon low-power photoirradiation. Suchrobust ROS cascades can not only provoke pronounced apoptotic damagetoward tumor cells, but also achieve nearly complete elimination ofsolid tumors in xenograft tumor-bearing mouse models. Moreover, Eu-TCPP displays a distinct photoluminescence turn-on responsetoward radioactive uranyl ions (UO22+). Thisstudy not only advances the crystal engineering of photosensitizersbuilt from lanthanide metal–organic frameworks (Ln-MOFs), butalso establishes a versatile paradigm for fabricating multifunctionalLn-MOF integrated theranostic platforms.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"65 41","pages":"24525–24534"},"PeriodicalIF":4.6,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149091953","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

Bulky BorylphosphidoComplexes of Iron and Cobaltwith N-Heterocyclic Carbene as an Ancillary Ligand 以n -杂环卡宾为辅助配体的铁钴大体积硼基磷化配合物

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-10-17 DOI: 10.1021/acs.inorgchem.6c04322

Wen Jiang,Tianqi Xia,Yujian Wang,Yichen Huang,Dongyang Wang,Xuebing Leng,Qi Chen,Liang Deng

{"title":"Bulky Borylphosphido\u0000Complexes of Iron and Cobalt\u0000with N-Heterocyclic Carbene as an Ancillary Ligand","authors":"Wen Jiang,Tianqi Xia,Yujian Wang,Yichen Huang,Dongyang Wang,Xuebing Leng,Qi Chen,Liang Deng","doi":"10.1021/acs.inorgchem.6c04322","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c04322","url":null,"abstract":"Abstract Terminal primary phosphido metal complexes are valuable synthetic reagents and intermediates for phosphination reactions and phosphinidene species. Their tendency to aggregate to form bridging phosphido complexes, however, poses a synthetic challenge. Herein, we show that the use of sterically demanding N-heterocyclic boryl-substituted phosphido and N-heterocyclic carbene (NHC) ligands allows access to terminal borylphosphido iron and cobalt complexes. The salt metathesis reactions of [(IAd)MCl(μ-Cl)]2 (M = Fe or Co; IAd = 1,3-diadamantylimidazol-2-ylidene) with 4 equiv of K[PH(NHB)] (NHB = B(N(Dipp)CHCHN(Dipp)); Dipp = 2,6-iPr2C6H3) afford three-coordinate metal primary bis(phosphido) complexes [(IAd)M(PH(NHB))2] (M = Fe (1-Fe) or Co (1-Co)). Spectroscopic, magnetic, and computational studies indicated that 1-Fe adopts an S = 2 ground state and 1-Co features an S = 3/2 state. Reactivity studies revealed that 1-Fe and 1-Co react with 2 equiv of 4-(dimethylamino)pyridine (DMAP) to form tetrahedral complexes [(DMAP)2M(PH(NHB))2] (M = Fe (2-Fe) or Co (2-Co)), and their interaction with the 2,4,6-tri-tert-butylphenoxyl radical (SMesO•, 2 equiv) leads to P–P bond-forming reductive elimination to yield mononuclear iron(II) and cobalt(II) aryloxides [HIAd][Fe(OSMes)3] (3) and [(IAd)Co(OSMes)2] (4), along with diphosphine (NHB)HP-PH(NHB) (5).","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"12 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149210054","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