Organometallics最新文献

Synthesis of Type B Tetrazolylidene–Palladium Complexes and Comparative Analysis with a Type A Analog B型四氮吡啶-钯配合物的合成及其与a型类似物的比较分析

IF 2.9 3区化学

Organometallics Pub Date : 2025-09-10 DOI: 10.1021/acs.organomet.5c00277

Mirai Nakata, and , Tsunehisa Hirashita*,

引用次数: 0

Enhanced Stibine Oxide Lewis Basicity Overcomes Steric Frustration 增强氧化锑路易斯碱度克服位阻

IF 2.9 3区化学

Organometallics Pub Date : 2025-09-09 DOI: 10.1021/acs.organomet.5c00212

Addis Getahun, , , John S. Wenger, , and , Timothy C. Johnstone*,

{"title":"Enhanced Stibine Oxide Lewis Basicity Overcomes Steric Frustration","authors":"Addis Getahun, , , John S. Wenger, , and , Timothy C. Johnstone*, ","doi":"10.1021/acs.organomet.5c00212","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00212","url":null,"abstract":"The characteristic electronic structure of the phosphoryl group in phosphine oxides confers great stability on the P+–O– bond, in part because of back-bonding from O-based lone pairs into the P–C antibonding orbitals. The partial nature of this donation allows the O atom in the phosphoryl unit to exhibit Lewis basicity. This backbonding weakens as the atomic number of the pnictogen increases, which results in a significant enhancement in basicity for the heavier stiboryl congener. Here, we compare the ability of R3PnO (Pn = P, As, Sb) species to bind to main-group Lewis acids. As the steric bulk of the R group increases, R3PO and R3AsO lose this capacity; Dipp3PO and Dipp3AsO (where Dipp = 2,6-diisopropylphenyl) are unable to bind even the very strong Lewis acid B(C6F5)3. In contrast, the enhanced basicity of the stibine oxides allows them to overcome this steric hindrance and form adducts, even in the case of the very hindered Dipp3SbO·B(C6F5)3.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 18","pages":"2074–2082"},"PeriodicalIF":2.9,"publicationDate":"2025-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.organomet.5c00212","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145104098","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

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Pioneers and Influencers in Organometallic Chemistry: Professor Kyoko Nozaki, a Genuine Catalyst for Diverse Elements 有机金属化学的先驱和影响者：野崎恭子教授，多种元素的真正催化剂

IF 2.9 3区化学

Organometallics Pub Date : 2025-09-08 DOI: 10.1021/acs.organomet.5c00263

Takuya Kochi*,

引用次数: 0

Construction of Bimetallic and Trimetallic Aggregates with a [Y(COT)2]− Building Block: Solid-State Structures and Solution Behavior 用[Y(COT)2] -构筑块构建双金属和三金属聚集体：固态结构和溶液行为

IF 2.9 3区化学

Organometallics Pub Date : 2025-09-08 DOI: 10.1021/acs.organomet.5c00233

Zheng Zhou, , , Aaron J. Babson, , , Zheng Wei, , and , Marina A. Petrukhina*,

{"title":"Construction of Bimetallic and Trimetallic Aggregates with a [Y(COT)2]− Building Block: Solid-State Structures and Solution Behavior","authors":"Zheng Zhou, , , Aaron J. Babson, , , Zheng Wei, , and , Marina A. Petrukhina*, ","doi":"10.1021/acs.organomet.5c00233","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00233","url":null,"abstract":"Several new bimetallic and trimetallic complexes containing the [Y(COT)2]− unit in different coordination environments are synthesized and fully characterized using X-ray crystallography and NMR spectroscopy. These complexes include [K([2.2.2]cryptand)][Y(COT)2] (1), [K(18-crown-6)(THF)][Y(COT)2] (2), [Y2K2(COT)4(THF)4] (3), and [YKCa(COT)3(THF)3] (4). In the presence of secondary ligands, bimetallic ionic pairs that comprise a [Y(COT)2]− sandwich and a solvent-wrapped K+ ion are formed in 1 and 2. In contrast, 3 represents a bimetallic tetradecker oligomer with two [Y(COT)2]− units bridged by a K+ ion and a terminal [K(THF)4]+ moiety. Complex 4 is a heterotrimetallic triple-decker with an axial arrangement of three metal centers to form [Y(COT)2K(COT)Ca(THF)3]. Structural analysis shows the Y–COTcentroid distances in the [Y(COT)2]− sandwich are equidistant (1.884(6) Å) in 1 but become asymmetric in 2–4 (1.857(3)–1.952(3) Å), reflecting additional external coordination. The two COT rings are parallel in 1 and become increasingly tilted from 0.8 to 27.5° in 2–4, respectively. Multinuclear NMR spectroscopy measurements reveal the solution behavior of the sandwich and heterometallic multidecker COT-based products. The observed NMR spectroscopic trends corroborate with weak interactions between the [Y(COT)2]− unit and cationic moieties persisting in solutions of 2–4.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 18","pages":"2092–2098"},"PeriodicalIF":2.9,"publicationDate":"2025-09-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.organomet.5c00233","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145104066","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Anionic Property Is Crucial for the High Activities of Metalloligand Catalysts 阴离子性质是金属配体催化剂高活性的关键

IF 2.9 3区化学

Organometallics Pub Date : 2025-09-08 DOI: 10.1021/acs.organomet.5c00185

Lanbo Liu, , , Zhihui Li, , , Hao Lin, , , Wan Li, , , Xin Liu*, , , Zheng Wang*, , and , Longfei Li*,

{"title":"Anionic Property Is Crucial for the High Activities of Metalloligand Catalysts","authors":"Lanbo Liu, , , Zhihui Li, , , Hao Lin, , , Wan Li, , , Xin Liu*, , , Zheng Wang*, , and , Longfei Li*, ","doi":"10.1021/acs.organomet.5c00185","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00185","url":null,"abstract":"Metalloligand catalysts represent a significant class of catalysts, but the factors influencing the catalytic activity remain poorly understood, which presents a major challenge for their continued advancement. Herein, a comparative theoretical study is performed to investigate the CO2 hydrogenation facilitated by metalloligand catalysts. The anionic Co–Ga and Ni–Ga catalysts are predicted to exhibit very strong bond-activation abilities with low energy barriers, whereas their neutral Co–Ga and Ni–Ga congeners exhibit significantly weaker bond-activation capabilities and higher energy barriers to CO2 hydrogenations. The Lewis acidic character of the metalloligand is identified as a key factor contributing to the high energy barriers observed in neutral metalloligand catalysts. Moreover, the anionic nature of the catalysts can counteract the Lewis acidity of metalloligands, enhancing dπ basicity and promoting the catalytic activity of metalloligand catalysts. Guided by these insights, the anionic Rh–Ga catalyst RhGa1 is designed to facilitate CO2 hydrogenation with an energy span of 11.5 kcal/mol, representing a potential for high catalytic activity. The computational results suggest that the anionic nature is the determining factor for the low formate–metal binding free energies (ΔGbind) in anionic metalloligand catalysts.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 18","pages":"2055–2064"},"PeriodicalIF":2.9,"publicationDate":"2025-09-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145104040","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}

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Nonspectator Behavior of N-Heterocyclic Carbenes Directly Observed in High-Valent Copper Systems 高价铜体系中直接观察到的n -杂环碳烯的非旁观者行为

IF 2.9 3区化学

Organometallics Pub Date : 2025-09-06 DOI: 10.1021/acs.organomet.5c00309

Zehao Lu, , , Rui Feng, , , Guo Wang, , , Qian Zhou, , , Kai Li, , and , Shuai Guo*,

{"title":"Nonspectator Behavior of N-Heterocyclic Carbenes Directly Observed in High-Valent Copper Systems","authors":"Zehao Lu, , , Rui Feng, , , Guo Wang, , , Qian Zhou, , , Kai Li, , and , Shuai Guo*, ","doi":"10.1021/acs.organomet.5c00309","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00309","url":null,"abstract":"N-Heterocyclic carbenes (NHCs) have become highly popular ligands in modern copper chemistry, leading to the widespread application of Cu–NHCs in photoluminescent materials, catalysis, and biomedicine. In sharp contrast to copper(I) and copper(II) NHC complexes, examples of copper(III) NHCs are exceedingly rare. Synthetic methods for these complexes remain largely unexplored, and their reactivity is poorly understood. Additionally, although NHCs are typically considered spectator ligands, a longstanding debate persists regarding their potential nonspectator behavior at Cu(III), which is crucial for elucidating the true role of NHCs and for the rational design of Cu(III)/NHC systems. In this work, we present a rarely reported Cu(III) NHC system costabilized by CF3 donors. By exploring synthetic strategies, photo- and thermo-induced reactivity studies, as well as experimental and computational investigations, this study enables, for the first time, the direct observation of NHC-involved reactivity at Cu(III), along with relevant mechanistic insights.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 18","pages":"2118–2126"},"PeriodicalIF":2.9,"publicationDate":"2025-09-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145104094","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}

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Correction to “Half-Sandwich Ruthenium and Osmium Complexes with Hydrazinocurcuminoid-like Ligands” 更正“半夹心钌锇配合物与类肼姜黄素配体”

IF 2.9 3区化学

Organometallics Pub Date : 2025-09-05 DOI: 10.1021/acs.organomet.5c00319

Noemi Pagliaricci, , , Riccardo Pettinari*, , , Fabio Marchetti, , , Sara Pagliaricci, , , Massimiliano Cuccioloni, , , Anna Maria Eleuteri, , , Agustín Galindo, , , Farzaneh Fadaei-Tirani, , , Kseniya Glinkina, , and , Paul J. Dyson,

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Flash Communication: Cyclopropenium Radical Dication as an Outer-Sphere Oxidant for Group 10 Metal Complexes 闪光通讯：环丙烯自由基作为10族金属配合物的外球氧化剂

IF 2.9 3区化学

Organometallics Pub Date : 2025-09-05 DOI: 10.1021/acs.organomet.5c00269

Zoe E. Wachtel, , , Joshua Thedford, , , Sabrina N. Carneiro, , and , Melanie S. Sanford*,

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Tetramethylethylenediamine Stabilizes Organozinc Surface Intermediates against Chemical Etching but Not against Protodemetalation 四亚甲基二胺稳定有机锌表面中间体抗化学蚀刻，但不抗原脱金属作用。

IF 2.9 3区化学

Organometallics Pub Date : 2025-09-03 DOI: 10.1021/acs.organomet.5c00238

Hanyun Lou, and , Suzanne A. Blum*,

{"title":"Tetramethylethylenediamine Stabilizes Organozinc Surface Intermediates against Chemical Etching but Not against Protodemetalation","authors":"Hanyun Lou,  and , Suzanne A. Blum*, ","doi":"10.1021/acs.organomet.5c00238","DOIUrl":"10.1021/acs.organomet.5c00238","url":null,"abstract":"N,N,N’,N’-Tetramethylethylenediamine (TMEDA) is known to increase yields in Negishi-type cross-coupling reactions in aqueous–surfactant mixtures, presumably by increasing the persistence of the organozinc intermediates toward protodemetalation. The degree to which such stabilization enhances the key surface intermediates, however, is unknown. Here, the persistence of surface organozinc reaction intermediates was examined by fluorescence lifetime imaging microscopy. TMEDA did not increase the persistence of these oxidative addition intermediates toward protodemetalation by water in THF or DMF, indicating that its stabilizing effect may be limited to the solution phase. TMEDA, however, enhanced the persistence of these oxidative addition intermediates toward trimethylsilyl chloride and 1,2-dibromoethane, reagents commonly used in preparative organozinc reagent syntheses that presumably act through zinc surface etching. The data suggest that TMEDA hinders surface etching. The results pinpoint the elementary steps that result in enhanced water stability of organometallics for use in developing aqueous–organic reaction systems.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 18","pages":"1999–2002"},"PeriodicalIF":2.9,"publicationDate":"2025-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145038906","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}

引用次数: 0

N-Heterocyclic Carbene Ligand Effects on Pd-Catalyzed C–H Activation: A Computational Analysis n -杂环羰基配体对pd催化C-H活化的影响：计算分析

IF 2.9 3区化学

Organometallics Pub Date : 2025-09-01 DOI: 10.1021/acs.organomet.5c00184

Valiya P. Ummu Habeeba, , , Kavanal P. Prasanthkumar*, , and , Pookkottu K. Sajith*,

{"title":"N-Heterocyclic Carbene Ligand Effects on Pd-Catalyzed C–H Activation: A Computational Analysis","authors":"Valiya P. Ummu Habeeba, , , Kavanal P. Prasanthkumar*, , and , Pookkottu K. Sajith*, ","doi":"10.1021/acs.organomet.5c00184","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00184","url":null,"abstract":"C–H activation presents a sustainable strategy for direct inert C–H bond functionalization. This density functional theory (DFT) study examines methane activation by neutral and cationic Pd(II)-methoxy complexes via oxidative addition (OA) and σ-bond metathesis (SBM). We elucidate the trans effect and trans influence of 21 electronically and structurally diverse N-heterocyclic carbene (NHC) ligands in these processes. SBM pathways exhibited significantly lower activation energies (Ea) than OA pathways, with cationic complexes generally displaying higher barriers. Complexes containing NHCs with strongly electron-withdrawing substituents consistently showed lower Ea across all pathways, while those bearing electron-donating groups resulted in higher Ea. Electron-donating abilities of NHCs were quantified with electrostatic potential (ESP) parameters viz., molecular electrostatic potential minimum (Vmin), and potential at the carbene carbon nucleus (VC). Quantitative correlations were found between Ea and both Vmin and VC. Our results demonstrate that Vmin and VC serve as useful descriptors for analyzing the trans effect and trans influence of NHC ligands. This holds particularly true in systems lacking prominent secondary interactions and steric hindrance. These correlations highlight the critical role of NHC ligand design and offer a predictive framework to guide future catalyst optimization for alkane functionalization.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 18","pages":"2042–2054"},"PeriodicalIF":2.9,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145103977","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}

引用次数: 0