Organometallics最新文献

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A Nickel Pre-Catalyst for the O-Arylation of Primary, Secondary, and Tertiary Alcohols with (Hetero)aryl Chlorides 一种镍预催化剂用于伯、仲、叔醇与(杂)芳酰氯的o -芳化反应
IF 2.4 3区 化学
Organometallics Pub Date : 2026-10-12 Epub Date: 2026-09-25 DOI: 10.1021/acs.organomet.6c00313
Emily C. Jackson, Erika M. H. Elliott, Kathleen M. Morrison, Peter L. Fox, Katherine N. Robertson, Patrick L. DeRoy, Mark Stradiotto
{"title":"A Nickel Pre-Catalyst for the O-Arylation of Primary, Secondary, and Tertiary Alcohols with (Hetero)aryl Chlorides","authors":"Emily C. Jackson,&nbsp;Erika M. H. Elliott,&nbsp;Kathleen M. Morrison,&nbsp;Peter L. Fox,&nbsp;Katherine N. Robertson,&nbsp;Patrick L. DeRoy,&nbsp;Mark Stradiotto","doi":"10.1021/acs.organomet.6c00313","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00313","url":null,"abstract":"<p>While base metal-catalyzed cross-couplingsof alcohols and (hetero)arylchlorides have emerged over the past decade, the development of asingle pre-catalyst capable of promoting such transformations spanningall of primary, secondary, and tertiary (aliphatic) alcohols remainsan enduring challenge. Herein we disclose the easily prepared, air-stable4-cyanophenyl pre-catalyst (<strong>L2</strong>)Ni(4-CN-Ph)Cl (<strong>L2</strong> = CgPhen-DalPhos), which is shown to be capable of promoting, withuseful reaction scope, the C–O cross-coupling of all such alcoholclasses with (hetero)aryl chlorides.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 19","pages":"2266–2270"},"PeriodicalIF":2.4,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173572","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
Reactions of [Ru3(CO)10(μ-dppf)] with Internal Alkynes: A Fine Balance between C–H and P–C Oxidative-Addition to the Triruthenium Center [Ru3(CO)10(μ-dppf)]与内炔的反应:C-H和P-C氧化的精细平衡-三钌中心加成
IF 2.4 3区 化学
Organometallics Pub Date : 2026-10-12 Epub Date: 2026-09-30 DOI: 10.1021/acs.organomet.6c00224
Md. Arshad H. Chowdhury, Shahin A. Begum, Jagodish C. Sarker, Md. Monir Hossain, Subas Rajbangshi, Vladimir N. Nesterov, Graeme Hogarth, Shariff E. Kabir
{"title":"Reactions of [Ru3(CO)10(μ-dppf)] with Internal Alkynes: A Fine Balance between C–H and P–C Oxidative-Addition to the Triruthenium Center","authors":"Md. Arshad H. Chowdhury,&nbsp;Shahin A. Begum,&nbsp;Jagodish C. Sarker,&nbsp;Md. Monir Hossain,&nbsp;Subas Rajbangshi,&nbsp;Vladimir N. Nesterov,&nbsp;Graeme Hogarth,&nbsp;Shariff E. Kabir","doi":"10.1021/acs.organomet.6c00224","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00224","url":null,"abstract":"<p>The reactivity of[Ru<sub>3</sub>(CO)<sub>10</sub>(μ-dppf)](<strong>1</strong>) [dppf = 1,1′-bis(diphenylphosphino)ferrocene]toward internal alkynes, RC≡CR (<em>R</em> = Et, Ph,CO<sub>2</sub>Me, CO<sub>2</sub>Et), has been explored. Isolated productsvary with the nature of the alkyne substituent and differ from thosegenerated with related diphosphine-stabilized triruthenium clusters.In all products, one or two equivalents of alkyne are incorporatedand three or four carbonyls are lost. With hex-3-yne, the allenylcluster [Ru<sub>3</sub>(CO)<sub>7</sub>(μ-H)(μ-dppf)(μ<sub>3</sub>-η<sup>1</sup>:η<sup>2</sup>:η<sup>2</sup>-MeCHC≡CEt)] (<strong>2</strong>) results via aliphatic C–Hbond activation of one of the ethyl groups. With diphenylacetylene,the major product is [Ru<sub>3</sub>(CO)<sub>6</sub>(μ-H){μ-Ph<sub>2</sub>P(C<sub>5</sub>H<sub>3</sub>)Fe(C<sub>5</sub>H<sub>4</sub>)PPh<sub>2</sub>}(μ<sub>3</sub>-η<sup>1</sup>:η<sup>1</sup>:η<sup>2</sup>-PhC<sub>2</sub>Ph)] (<strong>3</strong>)which contains a capping alkyne ligand and a metalated dppf ligand,formed via C–H activation of one of the cyclopentadienyl rings.Metalation results in formation of a dative Fe–Ru bond. Withactivated alkynes (RCO<sub>2</sub>)C<sub>2</sub>(CO<sub>2</sub>R)(<em>R</em> = Me, Et), alkyne coupling occurs to afford theopen 52-electron clusters [Ru<sub>3</sub>(μ-CO)(CO)<sub>6</sub>(μ-PPh<sub>2</sub>){μ-η<sup>1</sup>:κ<sup>1</sup>-Ph<sub>2</sub>P(C<sub>5</sub>H<sub>4</sub>)Fe(C<sub>5</sub>H<sub>4</sub>)}{μ<sub>3</sub>-η<sup>1</sup>:η<sup>2</sup>:η<sup>2</sup>:κ<sup>1</sup>-C<sub>4</sub>(CO<sub>2</sub>R)<sub>4</sub>}] (<strong>4–5</strong>). The later containbridging phosphido (PPh<sub>2</sub>) and chelating Ph<sub>2</sub>PFe(C<sub>5</sub>H<sub>4</sub>)<sub>2</sub> ligands, formed via a previouslyunreported P–C bond cleavage of the coordinated dppf ligand.All four new clusters have been characterized by single-crystal X-raydiffraction studies. We discuss likely reaction pathways and why thesetransformations differ so much as a function of the appended diphosphineligand.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 19","pages":"2271–2278"},"PeriodicalIF":2.4,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173951","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
Flash Communication: Copper Complexes Supported by Macrocyclic N-Heterocyclic Carbene Ligands with Ether or Secondary Amine Donors 闪光通讯:由大环n杂环碳烯配体与醚或仲胺供体支持的铜配合物
IF 2.4 3区 化学
Organometallics Pub Date : 2026-10-12 Epub Date: 2026-09-22 DOI: 10.1021/acs.organomet.6c00208
Matthew O. Ariwoola, Paul Bekai, Soumyadip Sharangi, Brenna Lawrence, Kaden Moracco, Yunping Zhoujin, Mark D. Smith, Hans-Conrad zur Loye, Heui Beom Lee
{"title":"Flash Communication: Copper Complexes Supported by Macrocyclic N-Heterocyclic Carbene Ligands with Ether or Secondary Amine Donors","authors":"Matthew O. Ariwoola,&nbsp;Paul Bekai,&nbsp;Soumyadip Sharangi,&nbsp;Brenna Lawrence,&nbsp;Kaden Moracco,&nbsp;Yunping Zhoujin,&nbsp;Mark D. Smith,&nbsp;Hans-Conrad zur Loye,&nbsp;Heui Beom Lee","doi":"10.1021/acs.organomet.6c00208","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00208","url":null,"abstract":"<p>Metal complexes featuring secondary amine donors havebeen extensivelystudied in the context of hydrogen-bonding or metal–ligandcooperative interactions. In this regard, pincer-type ligand frameworkshave been described, but macrocyclic variants remain rare. Herein,we describe the synthesis of macrocyclic carbene ligand frameworksfeaturing a carbazolide backbone and an ether or secondary amine donor.While the ether was synthesized through conventional methods, theamine variant required microwave heating. Carbazolide-bis(imidazolium)pro-ligands were isolated as air-stable compounds. Metalation withCu(acac)<sub>2</sub> led to the formation of square-planar Cu(II)complexes characterized by single-crystal X-ray diffraction and cyclicvoltammetry. A significantly more cathodic Cu(I)/Cu(II) wave by 330mV was observed for the amine complex. Combined, the results highlightnew macrocyclic carbene platforms with variable coordination environments.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 19","pages":"2245–2249"},"PeriodicalIF":2.4,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173655","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
Constrained Geometry Catalysts in Ethylene Polymerization: From Mechanistic Understanding to High-Throughput Virtual Screening 乙烯聚合中的约束几何催化剂:从机理理解到高通量虚拟筛选
IF 2.4 3区 化学
Organometallics Pub Date : 2026-10-12 Epub Date: 2026-09-21 DOI: 10.1021/acs.organomet.6c00254
Shi-Yun Feng, Rui-Hong He, Xu-Bin Wang, Qi Yang, Jing-Shuang Dang
{"title":"Constrained Geometry Catalysts in Ethylene Polymerization: From Mechanistic Understanding to High-Throughput Virtual Screening","authors":"Shi-Yun Feng,&nbsp;Rui-Hong He,&nbsp;Xu-Bin Wang,&nbsp;Qi Yang,&nbsp;Jing-Shuang Dang","doi":"10.1021/acs.organomet.6c00254","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00254","url":null,"abstract":"<p>The rational design of constrained geometry catalysts(CGCs) forolefin polymerization remains challenging due to the intricate interplaybetween steric and electronic effects and the prohibitive computationalcost of exploring large chemical spaces using quantum-chemical methods.In this work, we develop a mechanistically informed machine learningframework that bridges semiempirical GFN2-xTB descriptors with densityfunctional theory (DFT)-computed activation barriers for ethyleneinsertion. DFT calculations identify the first insertion as the rate-determiningstep (RDS), enabling construction of a physically motivated surrogatemodel based on the cationic methyl active species. Benchmarking acrosseight regression algorithms identifies Gradient Boosting Regressoras the optimal predictor, delivering DFT-comparable predictive accuracywhile reducing computational cost by several orders of magnitude.SHapley Additive exPlanations analysis reveals that metal electrophilicityis the primary factor governing the activation barrier of the RDS,providing direct mechanistic interpretation of the learned structure–activityrelationships. Application of the model to a virtual library of approximately1.4 × 10<sup>5</sup> chemically valid CGCs via a high-throughputvirtual screening workflow rapidly identifies low-barrier candidatesand uncovers robust design principles, particularly the beneficialrole of electron-donating cyclopentadienyl substituents. The presentframework establishes an interpretable and efficient paradigm foraccelerated polyolefin catalyst discovery.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 19","pages":"2304–2313"},"PeriodicalIF":2.4,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173495","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
Chiral Rh Diene NHC Complexes and Their Application in Rh-Catalyzed Cycloisomerization of Enynes 手性Rh二烯NHC配合物及其在Rh催化炔环异构化中的应用
IF 2.4 3区 化学
Organometallics Pub Date : 2026-10-12 Epub Date: 2026-09-19 DOI: 10.1021/acs.organomet.6c00275
Derman Batman, Manuel Kirchhof, Severin Haid, Katrin Gugeler, Alexander Beck, Wolfgang Frey, Johanna Osterbrink, Biprajit Sarkar, Anna Zens, Johannes Kästner, Sabine Laschat
{"title":"Chiral Rh Diene NHC Complexes and Their Application in Rh-Catalyzed Cycloisomerization of Enynes","authors":"Derman Batman,&nbsp;Manuel Kirchhof,&nbsp;Severin Haid,&nbsp;Katrin Gugeler,&nbsp;Alexander Beck,&nbsp;Wolfgang Frey,&nbsp;Johanna Osterbrink,&nbsp;Biprajit Sarkar,&nbsp;Anna Zens,&nbsp;Johannes Kästner,&nbsp;Sabine Laschat","doi":"10.1021/acs.organomet.6c00275","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00275","url":null,"abstract":"<p>Chiral dienes and <em>N</em>-heterocyclic carbenes(NHC)are important ligands for transition-metal catalysis. Surprisingly,both ligand classes are rarely employed together in Rh complexes.To get more detailed insight into the interaction between NHC anddiene ligand simultaneously coordinated to the same Rh center, a seriesof eight neutral Rh diene NHC complexes, [Rh(L1)(NHC)Cl] (NHC = ICy,IMes, I<sup><em>i</em></sup>Pr, IPr, SIPr, IMe, (<em>R</em>)-IEtPh, and (<em>S</em>)-IEtPh), and four cationic analogues,[Rh(L1)(NHC)]X (NHC = ICy, IMes, IPr: X = B(Ar<sup>F</sup>)<sub>4</sub>; NHC = ICy: X = SbF<sub>6</sub>), were synthesized from [Rh(L1)Cl]by three complementary synthetic routes and anion exchange. X-raycrystal structure analyses revealed pronounced NHC-dependent distortionsfrom a square-planar geometry in neutral complexes, whereas cationicspecies remain comparatively rigid. Catalytic studies showed a strongdependence on the NHC ligand’s identity: while NHC incorporationgenerally reduced yields and enantioselectivities in asymmetric 1,2-and 1,4-additions, the cationic complex [Rh(L1)(ICy)]SbF<sub>6</sub> delivered improved activity and selectivity in 1,6-enyne cycloisomerization,consistent with reduced catalyst deactivation as confirmed by kineticanalysis. DFT calculations identified that stereocontrol originatesfrom key interactions enforced by the chiral diene scaffold, disruptedby bulkier NHC ligands. These findings highlight the decisive influenceof NHC sterics on the structure, stability, and asymmetric reactivityof Rh diene catalysts.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 19","pages":"2325–2340"},"PeriodicalIF":2.4,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173606","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
Reppe-Type Regioselective Assembly of Meta-Teraryls using Phenyl Vinyl Sulfone as a Traceless Acetylene Surrogate 以苯基乙烯基砜作为无迹乙炔替代物的间基芳基重复型区域选择性组装
IF 2.4 3区 化学
Organometallics Pub Date : 2026-10-12 Epub Date: 2026-09-25 DOI: 10.1021/acs.organomet.6c00212
Stephen M. Long, Emily L. Heller, Cody A. Tolliver, Brian S. Dolinar, Gregory B. Dudley, Brian V. Popp
{"title":"Reppe-Type Regioselective Assembly of Meta-Teraryls using Phenyl Vinyl Sulfone as a Traceless Acetylene Surrogate","authors":"Stephen M. Long,&nbsp;Emily L. Heller,&nbsp;Cody A. Tolliver,&nbsp;Brian S. Dolinar,&nbsp;Gregory B. Dudley,&nbsp;Brian V. Popp","doi":"10.1021/acs.organomet.6c00212","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00212","url":null,"abstract":"<p>Benzene rings are among the most frequently encounteredring systemsin small-molecule drugs, but only a few substitution patterns (1-,1,2-, 1,4-, and 1,2,4-) predominate. Here, regioselective nickel-catalyzedthree-component cyclotrimerization of terminal alkynes and phenylvinyl sulfone was used to synthesize an underrepresented substitutionpattern, the 1,3-arene. Phenyl vinyl sulfone serves as an acetylenesurrogate for the regiocontrolled synthesis of <em>meta</em>-terphenyl derivatives. The reaction demonstrated wide functionalgroup tolerance with moderate to good yields. Stoichiometric reactivitystudies with catalytically relevant nickel complexes established themechanistic origin of the observed regioselectivity.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 19","pages":"2250–2255"},"PeriodicalIF":2.4,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173755","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
Exploring the Generality of Post-Transition State Bifurcations for Metal-Catalyzed C–H Insertion Reactions that Form 4-Membered Rings 探索金属催化形成四元环的碳氢插入反应的过渡态后分叉的普遍性
IF 2.4 3区 化学
Organometallics Pub Date : 2026-10-12 Epub Date: 2026-09-11 DOI: 10.1021/acs.organomet.6c00238
Yumeng Cao, Dean J. Tantillo
{"title":"Exploring the Generality of Post-Transition State Bifurcations for Metal-Catalyzed C–H Insertion Reactions that Form 4-Membered Rings","authors":"Yumeng Cao,&nbsp;Dean J. Tantillo","doi":"10.1021/acs.organomet.6c00238","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00238","url":null,"abstract":"<p>Post-transition state bifurcations (PTSBs) previouslyhave beenidentified in dirhodium-catalyzed C–H insertion reactions thatform β-lactones, where a single transition structure providesdirect access to both insertion and fragmentation products. Here,we investigate whether this behavior is a general feature of metal-catalyzedC–H insertion reactions by extending the analysis to iridium-and ruthenium-based catalysts, amide (lactam-forming) substrates,and metal-free carbene reactions. Using quantum chemical calculations,ab initio molecular dynamics (AIMD) simulations, and principal componentanalysis (PCA)-based potential energy surface (PES) construction,we demonstrate that PTSBs are present across all types of metal-catalyzedsystems examined. Catalyst identity influences PES topography andproduct selectivity, with iridium-based systems showing greater selectivityfor lactone formation than ruthenium-based systems. For amide substrates,fragmentation proceeds via a two-step pathway through a discrete intermediatenot observed in the ester series. Collectively, these results establishPTSBs as a general feature of the reaction landscape for metal-catalyzedC–H insertion reactions that form 4-membered rings.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 19","pages":"2287–2296"},"PeriodicalIF":2.4,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173649","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
Flash Communication: Synthesis of Nickel-Lanthanide Sulfido-bridged Coordination Clusters Using an Acid–Base Interaction 闪光通讯:利用酸碱相互作用合成镍-镧系硫化物桥接配簇
IF 2.4 3区 化学
Organometallics Pub Date : 2026-10-12 Epub Date: 2026-09-23 DOI: 10.1021/acs.organomet.6c00280
Anastasiia Yu. Konokhova, Mikhail Yu. Afonin, Kristina A. Aidakova, Artem S. Bogomyakov, Artem G. Demkin, Taisiya S. Sukhikh, Nikolay B. Kompankov, Sergey N. Konchenko
{"title":"Flash Communication: Synthesis of Nickel-Lanthanide Sulfido-bridged Coordination Clusters Using an Acid–Base Interaction","authors":"Anastasiia Yu. Konokhova,&nbsp;Mikhail Yu. Afonin,&nbsp;Kristina A. Aidakova,&nbsp;Artem S. Bogomyakov,&nbsp;Artem G. Demkin,&nbsp;Taisiya S. Sukhikh,&nbsp;Nikolay B. Kompankov,&nbsp;Sergey N. Konchenko","doi":"10.1021/acs.organomet.6c00280","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00280","url":null,"abstract":"<p>The reactions between [Cp*<sub>2</sub>Ln(allyl)] and [(dppe)Ni(SH)<sub>2</sub>] (dppe = Ph<sub>2</sub>PCH<sub>2</sub>CH<sub>2</sub>PPh<sub>2</sub>) or [(POCOP<sup>iPr</sup>)Ni(SH)](POCOP<sup>iPr</sup> =C<sub>6</sub>H<sub>3</sub>(OP(<em><sup>i</sup></em>Pr)<sub>2</sub>)<sub>2</sub>) proceed as a classic acid–base interactionin which the nickel hydrosulfide complexes serve as typical Brønstedacids. In case of the dibasic acid [(dppe)Ni(SH)<sub>2</sub>] thereactions lead to tetrametal coordination clusters [{(dppe)Ni}<sub>2</sub>(μ<sub>3</sub>-S)<sub>4</sub>{LnCp*}<sub>2</sub>] (Ln= Dy (<strong>1</strong>), Ho (<strong>2</strong>)) and accompanied by eliminationof propene and Cp*H, while in case of monobasic acid [(POCOP<sup>iPr</sup>)Ni(SH)] only (allyl)<sup>−</sup> serves as a proton acceptorand the reactions result in formation of bimetal species [(POCOP<sup>iPr</sup>)Ni(μ-S){LnCp*<sub>2</sub>}] (Ln = Dy (<strong>3</strong>), Ho (<strong>4</strong>), Y (<strong>5</strong>)). Single-crystal X-raydiffraction (XRD) revealed correspondingly tetrametal and dimetalsulfido-bridged Ni/S/Ln frameworks, with the binuclear complexes exhibitingexceptionally short Ln–S bond distances. Magnetic measurementsof the Ni/Dy and Ni/Ho complexes showed that the Ni(II) centers arediamagnetic and that the magnetic behavior is governed by correspondinglanthanide ion(s). For <strong>3</strong> field-induced slow magneticrelaxation was observed, with an effective relaxation barrier of 22K.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 19","pages":"2261–2265"},"PeriodicalIF":2.4,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173635","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
Arylamide-Ligated Scandium Bis(alkyl) Complexes in the Ring-Opening Polymerization of Trimethylene Carbonate: Comparing the Reactivity of Mono- Versus Dinuclear Complexes 芳酰胺-连接钪双(烷基)配合物在碳酸三亚甲基开环聚合中的应用:单核与双核配合物的反应活性比较
IF 2.4 3区 化学
Organometallics Pub Date : 2026-10-12 Epub Date: 2026-09-24 DOI: 10.1021/acs.organomet.6c00283
Fang Ma, Manqin Xu, Wei Xu, Jue Chen, Yunjie Luo
{"title":"Arylamide-Ligated Scandium Bis(alkyl) Complexes in the Ring-Opening Polymerization of Trimethylene Carbonate: Comparing the Reactivity of Mono- Versus Dinuclear Complexes","authors":"Fang Ma,&nbsp;Manqin Xu,&nbsp;Wei Xu,&nbsp;Jue Chen,&nbsp;Yunjie Luo","doi":"10.1021/acs.organomet.6c00283","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00283","url":null,"abstract":"<p>Compared with mononuclear catalysts, dinuclear catalystsoftenexhibit synergistic effects between their two metal centers, offeringunique advantages in enhancing catalytic performance. In this work,an alkyl elimination strategy was employed to synthesize novel arylamidomono- and dinuclear scandium bis(alkyl) complexes. The phenyl-bridgedarylamido ancillary ligands (2,6-<sup><em>i</em></sup>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>)NH(C<sub>6</sub>H<sub>4</sub>)NH(C<sub>6</sub>H<sub>3</sub>-2,6-<sup><em>i</em></sup>Pr<sub>2</sub>) (<strong>HL</strong><sup><strong>1</strong></sup>) and [4,4′-(2,6-<sup><em>i</em></sup>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>NH)<sub>2</sub>][C<sub>6</sub>H<sub>4</sub>]<sub>2</sub> (<strong>HL</strong><sup><strong>2</strong></sup>) were reacted with Sc(CH<sub>2</sub>SiMe<sub>3</sub>)<sub>3</sub>(THF)<sub>2</sub> in a 1:2 molar ratio in THF,yielding the corresponding dinuclear complexes [1,4-(2,6-<sup><em>i</em></sup>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>N)<sub>2</sub>(C<sub>6</sub>H<sub>4</sub>)][Sc(CH<sub>2</sub>SiMe<sub>3</sub>)<sub>3</sub>(THF)]<sub>2</sub> (<strong>1</strong>) and [4,4′-(2,6-<sup><em>i</em></sup>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>N)<sub>2</sub>(C<sub>6</sub>H<sub>4</sub>)<sub>2</sub>][Sc(CH<sub>2</sub>SiMe<sub>3</sub>)<sub>2</sub>(THF)<sub>2</sub>]<sub>2</sub> (<strong>2</strong>). To investigate the differences in polymerization performancebetween mononuclear and dinuclear complexes, the mononuclear arylamidoscandium bis(alkyl) complex [(2,6-<sup><em>i</em></sup>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>)N(C<sub>6</sub>H<sub>5</sub>)]Sc(CH<sub>2</sub>SiMe<sub>3</sub>)<sub>2</sub>(THF) (<strong>3</strong>) was preparedby reacting (2,6-<sup><em>i</em></sup>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>)NH(C<sub>6</sub>H<sub>5</sub>) (<strong>HL</strong><sup><strong>3</strong></sup>) with Sc(CH<sub>2</sub>SiMe<sub>3</sub>)<sub>3</sub>(THF)<sub>2</sub> in a 1:1 molar ratio in hexane. Allcomplexes were characterized by NMR spectroscopy and elemental analysis.Furthermore, the molecular structures of complexes <strong>1</strong> and <strong>2</strong> were unambiguously determined by single-crystal X-ray diffraction.All complexes were able to initiate the ring-opening polymerization(ROP) of trimethylene carbonate (TMC) with high activity under mildconditions. Compared to the mononuclear complex <strong>3</strong>, complex <strong>1</strong> displayed a distinct dinuclear synergistic effect on TMCpolymerization. Complex <strong>1</strong> enabled the ROP of TMC in amolecular-weight-controllable manner, allowing for the synthesis ofhigh-molecular-weight PTMC (<em>M</em><sub>n</sub> &gt; 10<sup>5</sup> g/mol) by tuning the monomer-to-initiator molar ratio.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 19","pages":"2359–2367"},"PeriodicalIF":2.4,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173749","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
Flash Communication: Microwave-Assisted Synthesis of 2-Alkylphenyl-Substituted (NHC)CuCl Complexes 闪光通信:微波辅助合成2-烷基苯基取代(NHC)CuCl配合物
IF 2.4 3区 化学
Organometallics Pub Date : 2026-10-12 Epub Date: 2026-09-24 DOI: 10.1021/acs.organomet.6c00276
Takumi Tsushima, Sakiha Kobayashi, Masaaki Nakamoto, Takuya Michiyuki, Hiroto Yoshida
{"title":"Flash Communication: Microwave-Assisted Synthesis of 2-Alkylphenyl-Substituted (NHC)CuCl Complexes","authors":"Takumi Tsushima,&nbsp;Sakiha Kobayashi,&nbsp;Masaaki Nakamoto,&nbsp;Takuya Michiyuki,&nbsp;Hiroto Yoshida","doi":"10.1021/acs.organomet.6c00276","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00276","url":null,"abstract":"<p>A base-free, microwave-assisted protocol using Cu<sub>2</sub>Oand NHC·HCl salts is reported, which allows the synthesis ofsterically less hindered 2-alkylphenyl-substituted (NHC)CuCl complexes,(SIMe<sup><em>ortho</em></sup>)CuCl, (SIPr<sup><em>ortho</em></sup>)CuCl, (IMe<sup><em>ortho</em></sup>)CuCl and (IPr<sup><em>ortho</em></sup>)CuCl; the use of dichloromethane inplace of conventionally used tetrahydrofuran as a solvent is the keyto success. Structural and NMR analyses show that 2-alkylphenyl substitutionefficiently modulates the steric properties of the (NHC)CuCl complexeswhile largely preserving the electronic properties of the NHC ligands.This work offers a useful strategy for designing diverse NHC ligands,providing a straightforward approach to sterically tunable (NHC)CuClcomplexes.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 19","pages":"2256–2260"},"PeriodicalIF":2.4,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173754","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
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