Organometallics最新文献_第2页

Heteroleptic Silver(I) Complexes of Dithiocarbamate and Phosphine Ligands: Synthesis, Characterization, and Their Application in Multicomponent Organic Reactions 二硫代氨基甲酸酯和膦配体杂电性银(I)配合物：合成、表征及其在多组分有机反应中的应用

IF 2.4 3区化学

Organometallics Pub Date : 2026-10-26 Epub Date: 2026-10-06 DOI: 10.1021/acs.organomet.6c00226

Ujala Maddheshiya, Sourav Mandal, Chote Lal Yadav, Kamlesh Kumar

{"title":"Heteroleptic Silver(I) Complexes of Dithiocarbamate and Phosphine Ligands: Synthesis, Characterization, and Their Application in Multicomponent Organic Reactions","authors":"Ujala Maddheshiya, Sourav Mandal, Chote Lal Yadav, Kamlesh Kumar","doi":"10.1021/acs.organomet.6c00226","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00226","url":null,"abstract":"Silver(I) complexes incorporating soft donor ligandssuch as dithiocarbamatesand phosphines have attracted considerable attention owing to theirdiverse structural features and notable catalytic activities. In thisstudy, a series of heteroleptic Ag(I) complexes with the general formula[Ag(I)(PPh3)2(L1-L3)] (C1–C3) were quantitatively synthesized using designed dithiocarbamateligand salts (KL1–KL3), where L1 = N,N-dibenzyl dithiocarbamate, L2 = N-ferrocenylmethyl-N-benzyldithiocarbamate, L3 = N-ferrocenylmethyl-N-3-methylpyridyl dithiocarbamate, in combination with triphenylphosphineas a coligand. All heteroleptic Ag(I) complexes were characterizedby Fourier transform infrared (FT–IR), ultraviolet–visible(UV–vis), multinuclear NMR, high-resolution mass spectra (HRMS),and elemental analyses. The solid-state structures of complexes C1 and C3 are confirmed by single-crystal X-raydiffraction (SCXRD). The X-ray structures revealed a distorted tetrahedralAgP2S2 coordination environment with a bidentatedithiocarbamate ligand and two PPh3 ligands. The catalyticpotentials of C1–C3 were subsequently investigatedin one-pot multicomponent organic transformations, enabling the efficientsynthesis of benzopyranopyrimidine and propargylamine derivatives,which are valuable heterocyclic and biologically relevant organicmolecules. The optimized conditions afforded the corresponding productsin good to excellent yields, demonstrating the ability of the Ag(I)heteroleptic complexes of dithiocarbamate and phosphine ligands topromote multicomponent C–C/C–N bond-forming processesefficiently under mild reaction conditions.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 20","pages":"2468–2481"},"PeriodicalIF":2.4,"publicationDate":"2026-10-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149281984","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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Flash Communication: Transfer Hydrogenation of Formic Acid to Methanol 闪光通讯：甲酸加氢转化为甲醇

IF 2.4 3区化学

Organometallics Pub Date : 2026-10-26 Epub Date: 2026-10-08 DOI: 10.1021/acs.organomet.6c00330

Ritu Bhardwaj, Abhishek Kumar, Joyanta Choudhury

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Cooperative N2 Reduction across a Multinuclear First-Row Transition Metal Platform 跨多核第一排过渡金属平台的协同N2还原

IF 2.4 3区化学

Organometallics Pub Date : 2026-10-26 Epub Date: 2026-10-14 DOI: 10.1021/acs.organomet.6c00206

Sultana P. Rumi, Jacob Hirschi, Bavita Kumari, Isabella F. Vedro, Isabella Mc Coll, Lev N. Zakharov, Tim J. Zuehlsdorff, Addison N. Desnoyer

{"title":"Cooperative N2 Reduction across a Multinuclear First-Row Transition Metal Platform","authors":"Sultana P. Rumi, Jacob Hirschi, Bavita Kumari, Isabella F. Vedro, Isabella Mc Coll, Lev N. Zakharov, Tim J. Zuehlsdorff, Addison N. Desnoyer","doi":"10.1021/acs.organomet.6c00206","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00206","url":null,"abstract":"The development ofmolecular systems capable of dinitrogen (N2) activationand reduction under mild conditions remains acentral challenge in inorganic chemistry. Herein, we report the synthesis,structures, and reactivity of a series of multimetallic first-rowtransition metal complexes supported by sterically encumbered tetraamidodiamine(TADA) ligands. Systematic variation of the silyl substituents enablesmodulation of ligand sterics while preserving the conformational flexibilityof the TADA scaffold, resulting in a diverse set of bimetallic andtetrametallic architectures. Structural studies reveal that increasedsteric bulk disfavors formation of previously reported syn closed geometries and instead promotes higher nuclearity assemblies,including ate complexes. These complexes were evaluated as precatalystsfor N2 reduction under standard silylation conditions (KC8/TMSCl), revealing a dependence of catalytic activity on metalidentity, nuclearity, reductant, and ligand sterics. Catalytic activitywas found to depend on metal identity in a manner not simply correlatedwith ligand sterics, with turnover numbers of up to 40. Stoichiometricreduction of a dititanium precursor affords a crystallographicallycharacterized, four-electron reduced product featuring substantialN–N bond elongation and asymmetric Ti environments. Densityfunctional theory calculations support a description of this speciesas a highly activated N24– unit stabilizedby π-backbonding and alkali metal interactions.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 20","pages":"2445–2453"},"PeriodicalIF":2.4,"publicationDate":"2026-10-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149282056","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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Ag(I)-Induced C–C Reductive Elimination from Pt(II): Role of Ag(I) and Counteranion Ag(I)诱导Pt（II）的C-C还原消除：Ag(I)和反阴离子的作用

IF 2.4 3区化学

Organometallics Pub Date : 2026-10-26 Epub Date: 2026-10-15 DOI: 10.1021/acs.organomet.6c00318

Md Asmaul Hoque, Zoë M. Gehman, Farzad Bastani, Jonah G. Clark, Kevin P. Quirion, Aakashi Jain, Diane A. Dickie, Amrit Venkatesh, Petra Reinke, Daniel H. Ess, T. Brent Gunnoe

{"title":"Ag(I)-Induced C–C Reductive Elimination from Pt(II): Role of Ag(I) and Counteranion","authors":"Md Asmaul Hoque, Zoë M. Gehman, Farzad Bastani, Jonah G. Clark, Kevin P. Quirion, Aakashi Jain, Diane A. Dickie, Amrit Venkatesh, Petra Reinke, Daniel H. Ess, T. Brent Gunnoe","doi":"10.1021/acs.organomet.6c00318","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00318","url":null,"abstract":"Transition-metal-catalyzedC–C bond formation,includingC–H functionalization reactions, often benefits from Lewisacid additives, among which Ag(I) salts are widely used in Pd-catalyzedtransformations. Despite this, direct experimental evidence definingthe mechanistic role of Lewis acid additives remains limited. Herein,we investigate the role of Ag(I) additives in C–C bond formationusing (6-Fp)PtPh2 (1) (6-Fp = 8,8′-(1,2-phenylene)diquinoline)as the starting complex. The reaction of (6-Fp)PtPh2 withdifferent Ag(I) compounds gives significantly different yields forthe formation of biphenyl. Unexpectedly, our combined experimental,including 195Pt NMR spectroscopy and X-ray photoelectronspectroscopy, and computational studies reveal that Ag(I) becomesincorporated into the Pt bonding framework to form multimetallic Pt/Agintermediates that can promote reductive elimination. The Ag(I) counteranionstrongly influences the structure and reactivity of these intermediates,giving the rate trend AgTFA ≈ AgOTf > AgNO3 forthe formation of biphenyl. These findings provide direct evidencefor multimetallic cooperation involving Ag(I) in C–C bond formation.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 20","pages":"2533–2545"},"PeriodicalIF":2.4,"publicationDate":"2026-10-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149282184","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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Synthesis and Reactivity Study of Metallaindole Complexes (M = Ru and Os) with a Fused Metallacyclopropene Unit 金属环丙烯熔融配合物（M = Ru和Os）的合成及反应性研究

IF 2.4 3区化学

Organometallics Pub Date : 2026-10-26 Epub Date: 2026-10-13 DOI: 10.1021/acs.organomet.6c00309

Qiwu Yu, Bingjie Fu, Yue Zhao, Lei Li, Wenfeng Jiang, Wei Bai

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Enhanced Optical Properties of a Cycloplatinated(II)–Thiolate Complex via Borane Coordination 硼烷配位增强环铂(II) -硫酸盐配合物的光学性质

IF 2.4 3区化学

Organometallics Pub Date : 2026-10-26 Epub Date: 2026-10-14 DOI: 10.1021/acs.organomet.6c00264

Zahra Ahmadi Khamesi, Hamid R. Shahsavari

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Visible-Light-Driven C–F Bond Cleavage in Perfluoroalkyl Carboxylic Acids: Readily Accessible Ruthenium-Bipyridine Complexes as Effective Catalysts 全氟烷基羧酸中可见光驱动的C-F键裂解：易接近的钌-联吡啶配合物作为有效催化剂

IF 2.4 3区化学

Organometallics Pub Date : 2026-10-26 Epub Date: 2026-10-14 DOI: 10.1021/acs.organomet.6c00279

Ashan S. Wickramaarachchi, Ishan D. Jayampathi, Maggie M. Larson, Alexander N. Erickson, Dian Wang

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Hydrosilane-Free Access to Iridium-NNSi Catalysts via Activation of Unstrained Si–C Bonds for C(sp3)–H Borylation C(sp3) -H硼化反应中无氢硅烷活化Si-C键制备铱- nnsi催化剂

IF 2.4 3区化学

Organometallics Pub Date : 2026-10-26 Epub Date: 2026-10-06 DOI: 10.1021/acs.organomet.6c00311

Takeru Torigoe, Satoko Okuda, Toshimichi Ohmura

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Fathoming Synthesis Strategies for Rare-Earth-Metal Trimethyl Compounds 稀土金属三甲基化合物合成策略探索

IF 2.4 3区化学

Organometallics Pub Date : 2026-10-26 Epub Date: 2026-10-01 DOI: 10.1021/acs.organomet.6c00282

Dorothea Schädle, Jakob Lebon, Berfin-K. Özer, Alexandros Mortis, Theresa E. Rieser, Melanie Meermann-Zimmermann, Karl W. Törnroos, Cäcilia Maichle-Mössmer, Reiner Anwander

{"title":"Fathoming Synthesis Strategies for Rare-Earth-Metal Trimethyl Compounds","authors":"Dorothea Schädle, Jakob Lebon, Berfin-K. Özer, Alexandros Mortis, Theresa E. Rieser, Melanie Meermann-Zimmermann, Karl W. Törnroos, Cäcilia Maichle-Mössmer, Reiner Anwander","doi":"10.1021/acs.organomet.6c00282","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00282","url":null,"abstract":"Thesynthesis of alkali-metal-free compounds [LnMe3]n is scrutinized using two distinct protocols.The donor-promoted cleavage of homoleptic tetramethylaluminate complexesLn(AlMe4)3 proves rare-earth metal (Ln) size-dependentand gives access to [LnMe3]n (small to midsized Ln(III)) and [LnMe3-x(AlMe4)x(OEt2)y] (large Ln(III)). Both compounds can beconverted to homoleptic tetramethylgallates Ln(GaMe4)3 by addition of trimethylgallium. Crystallization attemptsof [LnMe3-x(AlMe4)x(OEt2)y] viaextended donor-solvent treatment produced structural snapshots ofa diverse set of clusters featuring different stages of methyl groupdegradation. New homometallic coordination motifs are detected forcarbides [(C4−)(Ln3+)4] (Ln= La, Nd) and [(C4−)(Gd3+)6] as well as methylidyne [(CH3−)(Nd3+)5]. Applying the salt-metathesis protocol (Me3TACN)LnCl3(THF)x (x = 0, 1)/MeLi the discrete monomeric 6-coordinate (Me3TACN)LnMe3 (Ln = Dy, Er, Tm) and 7-coordinate (Me3TACN)LnMe3(THF) (Ln = La, Ce) can be obtained (Me3TACN = 1,4,7-trimethyl-1,4,7-triazacyclononane). IncompleteCl/CH3 exchange to afford mixed methyl/chloride complexes(Me3TACN)LnMe3-xClx was observed for praseodymium, neodymium, and samarium.Crystal structures of most of the new complexes have been obtainedand are discussed along with the findings from NMR studies.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 20","pages":"2498–2508"},"PeriodicalIF":2.4,"publicationDate":"2026-10-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149251320","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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Ligand-Derived Effects in N,C-Cyclometalated Palladium(II) Acetate Dimers 配体衍生的N， c -环金属化醋酸钯二聚体效应

IF 2.4 3区化学

Organometallics Pub Date : 2026-10-26 Epub Date: 2026-10-09 DOI: 10.1021/acs.organomet.6c00316

Jarosław Fornalski, Adrianna Gumienna, Bartłomiej Pigulski, Paweł Szlufik, Sławomir Szafert, Nurbey Gulia

{"title":"Ligand-Derived Effects in N,C-Cyclometalated Palladium(II) Acetate Dimers","authors":"Jarosław Fornalski, Adrianna Gumienna, Bartłomiej Pigulski, Paweł Szlufik, Sławomir Szafert, Nurbey Gulia","doi":"10.1021/acs.organomet.6c00316","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00316","url":null,"abstract":"N,C-Cyclometalatedpalladium(II)acetate dimers were synthesized as structurally related families differingby aryl ring substitution Pd1 or azole modification Pd2–5. X-ray study confirmed an acetate-bridged dimericscaffold, a pronounced structural trans influence, and systematicdifferences in steric congestion between the two series. SolutionNMR studies showed that Pd1 complexes exist predominantlyas a single transoid isomer, whereas Pd2–5 exhibits transoid/cisoid mixtures.Analysis of structural parameters and NMR data indicates that stericeffects and trans influence differentiation govern the transoid/cisoid ratio. In the cisoid form,the trans influence is concentrated on a single acetate bridge, weakeningthis trans-OAc ligand. Electrochemical studies (DPV/CV)revealed pronounced sensitivity of the first oxidation process toligand substitution, particularly within the Pd1 series,where an anodic shift of 0.37 V was observed. Correlation of oxidationpotentials with Hammett parameters and DFT-calculated frontier-orbitalenergies revealed substantial involvement of the cyclometalated arylring in oxidation. DFT calculations showed greater aryl contributionto the HOMO in Pd1 than in Pd2–5,providing an electronic basis for the strong substituent dependenceof oxidation. Positive correlations between oxidation potential andPd–Pd distance (or interplanar angle) indicate that stericeffects opposing Pd–Pd contraction disfavor oxidation.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 20","pages":"2518–2532"},"PeriodicalIF":2.4,"publicationDate":"2026-10-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149282092","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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