Organometallics最新文献_第2页

Formaldehyde with Methanol Outperforms Methanol in Ru(II)-Catalyzed C-Methylation of Ketones Ru（II）催化酮体c -甲基化反应中甲醛与甲醇的反应优于甲醇

IF 2.4 3区化学

Organometallics Pub Date : 2026-10-12 Epub Date: 2026-09-23 DOI: 10.1021/acs.organomet.6c00301

Manohar Shivaji Padmor, Sandip Bapu Khatal, Sanjay Pratihar

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Reactivity of a Bis(alkynyl)-Vinylidene Osmium Complex: Access to Carbynes, Vinyl Ester Derivatives, and C–C and C–N Bond-Forming Reactions 双炔基-偏乙烯锇配合物的反应性：碳炔、乙烯基酯衍生物及C-C和C-N键形成反应

IF 2.4 3区化学

Organometallics Pub Date : 2026-10-12 Epub Date: 2026-09-22 DOI: 10.1021/acs.organomet.6c00277

Sheila G. Curto, Joaquín M. Granados, Enrique Oñate, Montserrat Oliván

{"title":"Reactivity of a Bis(alkynyl)-Vinylidene Osmium Complex: Access to Carbynes, Vinyl Ester Derivatives, and C–C and C–N Bond-Forming Reactions","authors":"Sheila G. Curto, Joaquín M. Granados, Enrique Oñate, Montserrat Oliván","doi":"10.1021/acs.organomet.6c00277","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00277","url":null,"abstract":"Hexahydride OsH6(PiPr3)2 (1)reacts with tert-butylacetyleneto yield bis(alkynyl)-vinylidene Os(C≡CtBu)2(=C=CHtBu)(PiPr3)2 (2). Subsequent protonation of 2 withHOTf or Et3N·3HF affords the bis(alkynyl)-carbynederivatives [Os(C≡CtBu)2(≡CCH2tBu)(PiPr3)2]OTf(3) and OsF(C≡CtBu)2(≡CCH2tBu)(PiPr3)2 (4), respectively. In contrast, treatment of 2 with acetic acid leads to the alkynyl-vinylidene-vinyl ester derivativeOs(C≡CtBu){κ2-O,C-OC(CH3)OC=CHtBu}(=C=CHtBu)(PiPr3)2 (5). Density functionaltheory (DFT) calculations, together with deuterium labeling experiments,demonstrate that the protonation may occur either at the Cβ carbon of the vinylidene ligand or at the Cβ carbonatom of one of the alkynyl groups, and that the formation of 5 is governed by thermodynamic control. The reaction of 2 with 2-aminopyridine provides a new route for the selectivesynthesis of a 2,3-disubstituted imidazo[1,2-a]pyridinederivative starting from tert-butylacetylene and2-aminopyridine.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 19","pages":"2341–2349"},"PeriodicalIF":2.4,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173653","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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Syntheses and Structures of Solvent-Free bis(Trimethylsilyl)methyl Complexes of the Heavy Alkaline-Earth Metals 重碱土金属无溶剂双（三甲基硅基）甲基配合物的合成与结构

IF 2.4 3区化学

Organometallics Pub Date : 2026-10-12 Epub Date: 2026-09-20 DOI: 10.1021/acs.organomet.6c00241

Angus C. G. Shephard, Dawid Jędrzkiewicz, Bastian Rösch, Jens Langer, Christian Färber, Sjoerd Harder

{"title":"Syntheses and Structures of Solvent-Free bis(Trimethylsilyl)methyl Complexes of the Heavy Alkaline-Earth Metals","authors":"Angus C. G. Shephard, Dawid Jędrzkiewicz, Bastian Rösch, Jens Langer, Christian Färber, Sjoerd Harder","doi":"10.1021/acs.organomet.6c00241","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00241","url":null,"abstract":"Ether-free alkylmetal reagents are important precursorsin organometallicchemistry. With few exceptions, there are hardly any heavier, ether-freegroup 2 alkylmetal complexes. Herein we describe facile syntheticmethods for the synthesis of solvent-free Ae[CH(SiMe3)2]2 complexes (Ae = Ca, Sr, Ba) and discuss theirstructural and spectroscopic features. All complexes can be synthesizedby salt metathesis procedures. Reaction of two equivalents of KCH(SiMe3)2 with one equivalent of AeI2 in Et2O and subsequent removal of all solvents under high vacuumgave ether-free Ae[CH(SiMe3)2]2 inyields of 78% (Ca), 56% (Sr) and 80% (Ba).The Ca and Sr reagents couldalso be obtained by a solvent-free solid state synthetic route, i.e. by ball-milling KCH(SiMe3)2 andAeI2 in a 2:1 ratio and subsequent extraction by benzene.Facile access to highly reactive, ether-free heavier Ae metal alkylprecursors is important for further development of the rapidly growingfield of group 2 organometallic chemistry.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 19","pages":"2297–2303"},"PeriodicalIF":2.4,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173559","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

Mechanistic Elucidation of Silylation with Disilane via π-Allylpalladium Intermediates: Combined Experimentation and Automated Reaction Pathway Exploration π-烯丙基钯中间体与二硅烷硅基化反应机理的阐明：联合实验与自动反应途径探索

IF 2.4 3区化学

Organometallics Pub Date : 2026-10-12 Epub Date: 2026-09-26 DOI: 10.1021/acs.organomet.6c00281

Nobuki Katayama, Yasushi Obora

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Intermolecular Methyl-to-Magnesium Bonds in Organomagnesium Aggregates 有机镁团聚体中甲基-镁键的分子间研究

IF 2.4 3区化学

Organometallics Pub Date : 2026-10-12 Epub Date: 2026-09-24 DOI: 10.1021/acs.organomet.6c00267

Hangyu Zhou, Zixuan Wang, Qingzhong Li, Steve Scheiner

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Observation of Weak Driving-Force Dependence of Hydride Formation with Iron Carbonyl Clusters 羰基铁簇氢化物形成弱驱动力依赖性的观察

IF 2.4 3区化学

Organometallics Pub Date : 2026-10-12 Epub Date: 2026-09-22 DOI: 10.1021/acs.organomet.6c00228

Kevin Y. C. Lee, Franklin J. Guevara, Louise A. Berben

{"title":"Observation of Weak Driving-Force Dependence of Hydride Formation with Iron Carbonyl Clusters","authors":"Kevin Y. C. Lee, Franklin J. Guevara, Louise A. Berben","doi":"10.1021/acs.organomet.6c00228","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00228","url":null,"abstract":"Metal-hydrideformation reactions are common elementary reactionsin catalytic systems, including fuel formation and organic transformations.Here, metal-hydride formation rates with metal carbonyl clusters [Fe4N(CO)12]− and [Fe5N(CO)15]− were determined in MeCN andaqueous media using peak-shift analysis (PSA) and foot-of-the-waveanalysis (FOWA) performed on cyclic voltammetry data. In MeCN, hydrideformation exhibits exceptionally small dependence on the pKa of the proton source, as inferred from Brønstedslopes (α = 0.06 and 0.03) that are determined from plots ofPT rate vs pKa of the proton substrate.This indicates a minimal dependence of the PT rate on the drivingforce for the PT reaction. These values contrast with the larger slopescommonly observed for mononuclear transition-metal hydrides (α≈ 0.3–0.7). In aqueous solution, larger Brønstedslopes were observed (α = 0.54 and 0.23). Overall, these resultsdemonstrate that multinuclear metal clusters exhibit hydride-formationbehavior distinct from conventional single-site complexes. The abilityto maintain fast rates for metal-hydride formation under low driving-forceconditions may be a key feature that enables the previously reportedselective hydride transfer to CO2 by [Fe4N(CO)12]−.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 19","pages":"2279–2286"},"PeriodicalIF":2.4,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173769","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

Camphor-Based NHC Ruthenium Catalysts in AROCM: Influence of Catalyst Structure on Enantio- and E/Z Selectivity AROCM中樟脑基NHC钌催化剂：催化剂结构对映对和E/Z选择性的影响

IF 2.4 3区化学

Organometallics Pub Date : 2026-09-28 Epub Date: 2026-09-14 DOI: 10.1021/acs.organomet.6c00151

Daniel Kamzol, René Wilhelm

{"title":"Camphor-Based NHC Ruthenium Catalysts in AROCM: Influence of Catalyst Structure on Enantio- and E/Z Selectivity","authors":"Daniel Kamzol, René Wilhelm","doi":"10.1021/acs.organomet.6c00151","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00151","url":null,"abstract":"The development of stereoselective olefin metathesisremains akey challenge in modern catalysis, particularly in achieving simultaneouscontrol over the enantioselectivity and Z-selectivity.In this study, a new class of camphor-derived chiral NHC rutheniumcomplexes was designed, synthesized, and evaluated in asymmetric ring-openingcross-metathesis. Systematic modification of the ligand architectureenabled a detailed investigation of steric and electronic effectson catalytic performance. The prepared catalyst series exhibited highactivity in asymmetric ring-opening cross-metathesis (AROCM) reactions,with distinct trends observed between substituent size, catalyst reactivity,and stereoselectivity. While most complexes favored the formationof E-isomers, selected systems provided moderateto high enantioselectivity for Z products. Catechodithiolate-modifiedcatalysts displayed a significant enhancement in Z-selectivity and enantioselectivity, achieving up to 99% ee, albeit at the expense of the catalytic activity. Thesefindings highlight the critical role of ligand design in tuning catalystperformance and provide valuable insights into the structure–selectivityrelationships governing asymmetric Z-selective olefinmetathesis.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 18","pages":"2199–2208"},"PeriodicalIF":2.4,"publicationDate":"2026-09-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149067617","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

Synthesis of Rhodium and Ruthenium Pi-Complexes with Pendant Amide Substituents for Intramolecular Proton Transfer upon Activation of C–H Bonds 含挂式酰胺取代基的铑和钌pi配合物在活化碳氢键时的分子内质子转移的合成

IF 2.4 3区化学

Organometallics Pub Date : 2026-09-28 Epub Date: 2026-09-14 DOI: 10.1021/acs.organomet.6c00236

Tatiana N. Petrushina, Alevtina S. Voskresenskaia, Roman A. Pototskiy, Yulia V. Nelyubina, Dmitry S. Perekalin

引用次数: 0

Gram-Scale Synthesis and Crystallographic Characterization of the Trans-Spanning Bisphosphine PhTRAP and Aryl-Modified Analogs 跨跨双膦PhTRAP和芳基修饰类似物的克级合成和晶体学表征

IF 2.4 3区化学

Organometallics Pub Date : 2026-09-28 Epub Date: 2026-09-11 DOI: 10.1021/acs.organomet.6c00193

Shenghua Yang, Keary M. Engle

{"title":"Gram-Scale Synthesis and Crystallographic Characterization of the Trans-Spanning Bisphosphine PhTRAP and Aryl-Modified Analogs","authors":"Shenghua Yang, Keary M. Engle","doi":"10.1021/acs.organomet.6c00193","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00193","url":null,"abstract":"(S,S)-(R,R)-PhTRAP is a wide-bite-angle chiral bisphosphineinitiallyreported by Ito and co-workers; despite its unique coordination geometry,prior catalytic applications have been largely limited to enantioselectivehydrogenation and hydrosilylation. We recently leveraged the unique trans-spanning nature of this ligand in the Pd-catalyzedenantioselective anti-Michael (α-selective) hydroarylation ofunsaturated carbonyl compounds. Previously reported syntheses of thisligand employ hygroscopic phosphorus building blocks and sensitivelow-valent metal reagents and require hazardous reduction conditions,leading to operational challenges and variable yields. Here we describean alternative synthesis of PhTRAP employing mild conditions, affording(+)-PhTRAP on a gram scale in 41% yield over four steps from the readilyaccessible planar-chiral scaffold iodo-Ugi amine. We further applythis synthetic route to access two previously unreported aryl-modifiedanalogs in enantioenriched form, (S,S)-(R,R)-(3,5-Xyl)TRAP and (S,S)-(R,R)-(3,5-C6F2H3)TRAP. We determinedthe solid-state structures of this series of bisphosphines by X-raycrystallography and discuss the conformational differences acrossthis series.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 18","pages":"2185–2189"},"PeriodicalIF":2.4,"publicationDate":"2026-09-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149071162","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

Luminescent Three-Coordinate Copper(I) Complexes Supported by an 8-Aryl-1-Naphthyl-Substituted “Sandwich” NacNac Ligand 8-芳基-1-萘取代“三明治”NacNac配体负载的发光三坐标铜(I)配合物

IF 2.4 3区化学

Organometallics Pub Date : 2026-09-28 Epub Date: 2026-09-16 DOI: 10.1021/acs.organomet.6c00261

Ashish Kumar, Son N. T. Phan, Yen-Chu Lu, Kristine Klimovica, Thomas S. Teets

{"title":"Luminescent Three-Coordinate Copper(I) Complexes Supported by an 8-Aryl-1-Naphthyl-Substituted “Sandwich” NacNac Ligand","authors":"Ashish Kumar, Son N. T. Phan, Yen-Chu Lu, Kristine Klimovica, Thomas S. Teets","doi":"10.1021/acs.organomet.6c00261","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00261","url":null,"abstract":"Stericallyencumbered β-diketiminate (NacNac) ligands arewidely used in several contexts, and our group recently showed theyare effective at preventing excited-state distortion in copper(I)chromophores and increasing their lifetime. This work introduces compoundsbased on an 8-aryl-1-naphthyl-substituted “sandwich”NacNac ligand, hypothesized to impart even more steric protectionthan conventional NacNac ligands. We describe a series of Cu(I) heterolepticcompounds (Cu1–Cu7) where the “sandwich”NacNac ligand is paired with aryl isocyanides. The compounds are characterizedspectroscopically and by cyclic voltammetry, with the formal CuII/CuI redox potential occurring near the ferrocenecouple and minimally dependent on the isocyanide. In four crystallographicallycharacterized complexes, we observe percent buried volume (%Vbur) parameters of 67.4–71.6% for the“sandwich” NacNac, exceeding that of the common 2,6-diisopropylphenyl(Dipp) NacNac (%Vbur = 59.0–62.9%in related compounds). Despite the enhanced steric bulk, the compoundsare only photoluminescent at 77 K, which we attribute to the photophysicalnoninnocence of the 8-aryl-1-naphthyl groups, which quench the phosphorescenceat room temperature. Despite their photophysical limitations, thiswork suggests that such “sandwich” NacNac ligands areeffective at increasing the steric bulk around the metal center, whichcould be useful in applications in catalysis and small-molecule activation.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 18","pages":"2235–2244"},"PeriodicalIF":2.4,"publicationDate":"2026-09-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149067582","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