Organometallics最新文献_第6页

Effects of Increased Ligand Fields of the Second- and Third-Row Transition Metals on the Preferred Structures of Sandwich Compounds of Stoichiometry C12H12M 第二和第三行过渡金属配体场增加对化学计量C12H12M夹层化合物优选结构的影响

IF 2.4 3区化学

Organometallics Pub Date : 2026-08-24 Epub Date: 2026-07-31 DOI: 10.1021/acs.organomet.6c00202

Yongtao Liu, Haoyu Chen, Jinfeng Luo, Huidong Li, Zhixiang Fan, Qunchao Fan, R. Bruce King, Henry F. Schaefer, III

{"title":"Effects of Increased Ligand Fields of the Second- and Third-Row Transition Metals on the Preferred Structures of Sandwich Compounds of Stoichiometry C12H12M","authors":"Yongtao Liu, Haoyu Chen, Jinfeng Luo, Huidong Li, Zhixiang Fan, Qunchao Fan, R. Bruce King, Henry F. Schaefer, III","doi":"10.1021/acs.organomet.6c00202","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00202","url":null,"abstract":"The lowest-energy sandwich structures for the (CnHn)M(CmHm) (n = 5, 6; m = 7, 6; m + n = 12;M = Zr to Pd and Hf to Pt) systems are all singlet or doublet spinstate structures, reflecting the increased ligand-field strengthsof second- and third-row transition metals relative to first-row transitionmetals. For Groups 7 and 8, this differs from the first-row transitionmetals, for which the lowest energy C12H12Msandwich structures for iron and manganese are high-spin triplet andquartet-spin state dibenzene-metal (η6-C6H6)2M (M = Fe, Mn) structures, respectively.For palladium and platinum, the lowest-energy C12H12M (M = Pd, Pt) structures have two dihapto benzene ligandscoordinating to the central metal atom, each through only one of theirthree C═C double bonds. This contrasts with the nickel C12H12Ni system, in which a singlet spin state (η6-C6H6)Ni(η2-C6H6) structure having one hexahapto and one dihapto benzeneligand is strongly energetically preferred. Similar doublet-spin state(η6-C6H6)M(η2-C6H6) (M = Co, Rh, Ir) structures are energeticallypreferred for the three Group 9 metals. The energetically preferredstructures for all of the early transition metals are low-spin (η6-C6H6)2M and (η5-C5H5)M(η7-C7H7) structures, in which all 12 ring carbon atoms arebonded to the central metal atom.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 16","pages":"2018–2024"},"PeriodicalIF":2.4,"publicationDate":"2026-08-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148810297","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

Retraction of “Flash Communication: Temperature-Dependent Initiation Mechanism in AlCl3-Catalyzed Cationic Polymerization of Isobutylene” “闪光通讯：alcl3催化异丁烯阳离子聚合的温度依赖引发机制”的撤回

IF 2.4 3区化学

Organometallics Pub Date : 2026-08-24 Epub Date: 2026-08-03 DOI: 10.1021/acs.organomet.6c00232

Xinyi Yang, Jiongyi Chen, Fanyuan Zhang, Xindi Feng, Zhen Liu

引用次数: 0

Anticancer Potential of Camalexin-Derived Ru(II) Metallacycles camalexin衍生Ru（II）金属环的抗癌潜力

IF 2.4 3区化学

Organometallics Pub Date : 2026-08-24 Epub Date: 2026-08-08 DOI: 10.1021/acs.organomet.6c00152

Paul Getreuer, Dominik Wenisch, Dina Baier-Romfeld, Laura Marretta, Michaela Hejl, Fynnius Monarth, Soheil Mahmoudi, Alessio Terenzi, Michael A. Jakupec, Bernhard K. Keppler, Wolfgang Kandioller

{"title":"Anticancer Potential of Camalexin-Derived Ru(II) Metallacycles","authors":"Paul Getreuer, Dominik Wenisch, Dina Baier-Romfeld, Laura Marretta, Michaela Hejl, Fynnius Monarth, Soheil Mahmoudi, Alessio Terenzi, Michael A. Jakupec, Bernhard K. Keppler, Wolfgang Kandioller","doi":"10.1021/acs.organomet.6c00152","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00152","url":null,"abstract":"Camalexin, a primaryindole-analogous phytoalexin from Arabidopsis thaliana and other crucifers, inhibitsthe proliferation of various cancer cells. In this contribution, thesynthesis and characterization of camalexin-derived Ru(II) half-sandwichcomplexes are described. Formation and sufficient purity of the complexeswere confirmed by 1H-, 13C- and 2D-NMR techniques,X-ray or 3D electron diffractometry, high-resolution-mass-spectrometry(HRMS) and elemental analysis. Additionally, the stability in aqueoussolution was studied under pseudophysiological conditions, revealingsufficient stability for further biological studies. Investigatingthe in vitro anticancer potency by means of 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl-2H tetrazolium bromide (MTT) and resazurin assays in fourhuman cancer cell lines revealed IC50 values in the (mostlylow) micromolar range. Tests for the capacity of generating reactiveoxygen species (ROS) in the leukemic HL60 cell line identified onederivative with exceptionally high ROS induction via a 2′,7′-dichlorofluorescindiacetate (DCFH-DA)-based approach. While increased ROS levels werenot decisive for cell death induction, cytotoxic activity of the complexeswas associated with mitochondrial membrane depolarization and functionalperturbation. Lastly, the ability of the complexes to induce apoptosiswas investigated, with the complexes showing remarkable effects, whilethe free ligands exhibited hardly any signs of apoptosis induction.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 16","pages":"1947–1959"},"PeriodicalIF":2.4,"publicationDate":"2026-08-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148810070","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

Chalcogenophosphinites with a Cyclic Oligosilane Backbone 具有环状低聚硅烷骨架的硫原藻

IF 2.4 3区化学

Organometallics Pub Date : 2026-08-24 Epub Date: 2026-08-13 DOI: 10.1021/acs.organomet.6c00221

Clara A. Roller, Roland C. Fischer, Michaela Flock

{"title":"Chalcogenophosphinites with a Cyclic Oligosilane Backbone","authors":"Clara A. Roller, Roland C. Fischer, Michaela Flock","doi":"10.1021/acs.organomet.6c00221","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00221","url":null,"abstract":"A structurally authenticatedseries of chalcogenophosphinites,R2P(ChPh) (Ch = S, Se, Te), supported by a compact tetrasilaphosphacyclopentanebackbone, is presented. The parent secondary phosphane is obtainedin two scalable steps from a dichlorohexasilane via substitution with 2.0 eq. NaPH2 and intramolecular ring-closuredriven by PH3 elimination. Selective deprotonation furnisheslithium and potassium phosphides that serve as versatile entry pointsto functionalization. Reaction of the parent phosphane with PhChChPh(Ch = S, Se) yields the thio- and selenophosphinites, whereas employingthe potassium phosphide delivers the full S/Se/Te series in higheryields and provides access to the tellurium derivative that is notaccessible from the secondary phosphane. Across the series, 31P NMR shifts move markedly upfield in a nonlinear fashion (S →Se → Te), and UV/vis spectra exhibit progressive bathochromism;both trends are reproduced by DFT/TD-DFT and traced to HOMO–LUMOgap narrowing together with increasing polarizability and heavy-atomeffects down the group. Single-crystal X-ray data reveal systematiclengthening of P-Ch bonds and widening of Si–P–Ch angles.Together, these results provide a sterically constant platform thatenables direct S/Se/Te comparison and illuminates periodic trendsin neutral chalcogenophosphinites stabilized by an oligosilane backbone.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 16","pages":"2025–2035"},"PeriodicalIF":2.4,"publicationDate":"2026-08-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148810312","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

Mechanochemical Synthesis of [Rh(L)(acac)(CO] Complexes (L = N-Heterocyclic Carbene or Phosphine) [Rh(L)(acac)(CO)]配合物（L = n -杂环卡宾或膦）的机械化学合成

IF 2.4 3区化学

Organometallics Pub Date : 2026-08-24 Epub Date: 2026-08-05 DOI: 10.1021/acs.organomet.6c00195

Gianluca Carì, Steven P. Nolan, Catherine S. J. Cazin

引用次数: 0

Flash Communication: Effects of Extension of Lone-Pair Interactions via σ-Symmetric Orbitals through Nonbonded Atoms 闪光通信：σ对称轨道对非键原子间孤对相互作用扩展的影响

IF 2.4 3区化学

Organometallics Pub Date : 2026-08-24 Epub Date: 2026-08-10 DOI: 10.1021/acs.organomet.6c00159

Masaichi Saito, Hiroaki Kobayashi, Sakura Takahashi, Soshi Mibu, Yuki Takada, Shunsuke Furukawa, Kazuya Ishimura

引用次数: 0

Demonstrating the Chemoselective Lewis Acid Activity of Pyridine(Diimine) Bismuth Cations 证明吡啶（二亚胺）铋阳离子的化学选择性路易斯酸活性

IF 2.4 3区化学

Organometallics Pub Date : 2026-08-24 Epub Date: 2026-08-05 DOI: 10.1021/acs.organomet.6c00250

Anthony M. Alfaro, Valerie A. Schmidt

引用次数: 0

Electronically Tunable Imidazo[1,2-a]pyridine Mesoionic Carbenes for PEPPSI-type Palladium Catalysts 电子可调咪唑[1,2-a]吡啶介离子羰基peppsi型钯催化剂

IF 2.4 3区化学

Organometallics Pub Date : 2026-08-24 Epub Date: 2026-08-11 DOI: 10.1021/acs.organomet.6c00185

Wun-Jie Huang, Jhen-Yi Lee, Tzu-Ying Li, Yi-Heng Huang, Hon Man Lee

{"title":"Electronically Tunable Imidazo[1,2-a]pyridine Mesoionic Carbenes for PEPPSI-type Palladium Catalysts","authors":"Wun-Jie Huang, Jhen-Yi Lee, Tzu-Ying Li, Yi-Heng Huang, Hon Man Lee","doi":"10.1021/acs.organomet.6c00185","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00185","url":null,"abstract":"A seriesof PEPPSI-type palladium complexes, trans-PdI2(NHC)(pyridine),incorporating unsymmetrical imidazo[1,2-a]pyridine-derivedmesoionic carbene (MIC) ligands, wassynthesized and characterized by single-crystal X-ray diffractionand DFT analysis. The C3-aryl substituents significantly modulatethe electronic structure, whereas the associated steric effects arecomparatively small and largely directional. Frontier-orbital, NBO,CDA, and ETS-NOCV analyses show that Pd–NHC bonding is dominatedby σ-donation with a smaller but significant π-backbondingcontribution, and while wingtip substitution primarily influencesthe π-acceptor ability of the MIC ligands. The p-CF3-substituted complex affords the strongest overall(σ + π) Pd–C interactions in the Pd0 models and exhibits a lower calculated oxidative-addition barrierthan the normal NHC analogue, providing a mechanistic rationale forits improved catalytic performance. Steric analysis using %Vbur further reveals that the ostensibly bulky anthracenyl substituentimposes the smallest buried volume because of its perpendicular orientation,underscoring the importance of steric directionality. In direct C–Harylation of 1,2-dimethylimidazole, all MIC-supported PEPPSI complexesoutperform trans-PdI2(IMes)(py), with the p-CF3-substituted complex showing the highest efficiency at low catalystloading. These findings establish imidazo[1,2-a]pyridine-derivedMIC ligands as electronically tunable ligands for highly active PEPPSI-typepalladium catalysts.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 16","pages":"1969–1982"},"PeriodicalIF":2.4,"publicationDate":"2026-08-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148810293","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

ScanBury: An Automated Distance-Dependent Buried Volume Analysis Tool─Insights into Sterically Induced Structural Distortions in Bis(tritert-butylphenyl) m-Terphenyl Isocyanide Complexes ScanBury：一种自动距离依赖的埋藏体积分析工具──对双（三叔丁基苯基）间terphenyl异氰化物配合物中立体诱导结构扭曲的见解

IF 2.4 3区化学

Organometallics Pub Date : 2026-08-24 Epub Date: 2026-08-10 DOI: 10.1021/acs.organomet.6c00245

Sean P. Dunphy, Erin N. Lewis, Ritchie E. Hernandez, Milan Gembicky, Joshua S. Figueroa

引用次数: 0

Platinum(II)-Mediated C–H Bond Activation of Benzene Revisited: Mechanistic Insights by Microkinetic Modeling 铂（II）介导的苯的C-H键活化：微动力学模型的机理见解

IF 2.4 3区化学

Organometallics Pub Date : 2026-08-24 Epub Date: 2026-08-01 DOI: 10.1021/acs.organomet.6c00121

Gilles Stebens, Burkhard Butschke

{"title":"Platinum(II)-Mediated C–H Bond Activation of Benzene Revisited: Mechanistic Insights by Microkinetic Modeling","authors":"Gilles Stebens, Burkhard Butschke","doi":"10.1021/acs.organomet.6c00121","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00121","url":null,"abstract":"The ion/molecule reaction of thecoordinatively unsaturated, cationicPt(II) complex [(bipy)Pt(CH3)]+ (bipy = 2,2′-bipyridine)with benzene─originally investigated in mass-spectrometricgas-phase studies─has been successfully translated into solution.[(bipy)Pt(CH3)(solv)]+ (solv = H2O and 2,2,2-trifluoroethanol (TFE)) is generated in situ by protonation of [(bipy)Pt(CH3)2] in TFEin the presence of benzene. The resulting C–H bond activationreaction proceeds by an order of magnitude faster than for a closelyrelated Pt(II)-diimine complex. In reactions with C6D6, kinetic isotope effects are not observed, and the data identifysubstrate coordination as the rate-determining step. The isotopologuedistributions of the reaction products are analyzed by a microkineticmodel, enabling quantification of the relative energetics of methaneloss and reversible C–H bond activation. Moreover, subtle insightssuch as the number of back-and-forth steps prior to the finalizingmethane loss are elucidated. Counterions and the water concentrationdo not have an influence on the observed isotopic distributions, thusindicating that the isotopologue-determining steps are strictly intramolecular. Extensive H/D scrambling provides clearevidence for the pronounced stability of the involved methane complexes[(L)Pt(C6H5)(CH4)]+. Moreover,degenerate benzene exchange in the initially formed benzene complexes[(L)Pt(CH3)(C6H6)]+ significantlyinfluences the produced isotopologue distributions.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 16","pages":"1905–1919"},"PeriodicalIF":2.4,"publicationDate":"2026-08-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148810178","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