Organometallics最新文献_第2页

Synthesis, Characterization, and Catalytic Evaluation of Ruthenium Complexes Bearing Xanthinium-8-dithiocarboxylate Ligands Derived from Caffeine and Theophylline 含咖啡因和茶碱衍生的 8-二硫代羧酸黄嘌呤配体的钌配合物的合成、表征和催化评估

IF 2.8 3区化学

Organometallics Pub Date : 2024-09-16 DOI: 10.1021/acs.organomet.4c00315

François Mazars, Guillermo Zaragoza, Lionel Delaude

{"title":"Synthesis, Characterization, and Catalytic Evaluation of Ruthenium Complexes Bearing Xanthinium-8-dithiocarboxylate Ligands Derived from Caffeine and Theophylline","authors":"François Mazars, Guillermo Zaragoza, Lionel Delaude","doi":"10.1021/acs.organomet.4c00315","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00315","url":null,"abstract":"Various experimental procedures and purification techniques were applied to alkylate or arylate the N7 and N9 positions of caffeine and theophylline into xanthinium salts. These N-heterocyclic carbene (NHC) precursors were converted into xanthinium-8-dithiocarboxylate zwitterions using CS2 and either Cs2CO3 or NaOtBu. The NHC·CS2 betaines were employed as chelating ligands to prepare a wide variety of [RuX(p-cymene)(S2C·NHC)]Y (X = Cl, SAc; Y = Cl, PF6, [RuCl3(p-cymene)]) and [Ru(S2C·NHC)3]X2 (X = Cl, PF6) complexes that were characterized by NMR and HRMS. Moreover, the molecular structures of three betaines, one hetero-, and one homoleptic complex were determined by XRD. The catalytic potentials of all these complexes were investigated in the transfer hydrogenation of ketones with isopropanol, the synthesis of vinyl esters from benzoic acid and 1-hexyne, and the cyclopropanation of styrene with ethyl diazoacetate. The reduction of acetophenone into 1-phenylethanol was chosen as a model reaction for the former application. Monitoring the time course of this transformation showed that chelates bearing a NHC·CS2 ligand displayed an initial activity slightly higher than the analogous [RuCl2(p-cymene)(NHC)] complex. Contrastingly, for the last two catalytic processes, the Ru(S2C·NHC) chelates did not outperform their Ru–NHC counterparts.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.8,"publicationDate":"2024-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142254668","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

Direct Detection of Pt(IV) Phenyl Complexes upon Intermolecular Oxidative Addition of Aryl Halides and Selective Csp3–I versus Csp2–Csp3 and Csp3–Csp3 Bonds Reductive Elimination from N-Heterocyclic Carbene Pt(IV) Phenyl Complexes 分子间氧化添加芳基卤化物时直接检测铂(IV)苯基配合物，以及从 N-杂环碳烯铂(IV)苯基配合物中选择性还原消除 Csp3-I 与 Csp2-Csp3 和 Csp3-Csp3 键

IF 2.8 3区化学

Organometallics Pub Date : 2024-09-13 DOI: 10.1021/acs.organomet.4c00314

Nan Zhang, Weiying He, Kristof M. Altus, Brian O. Patrick, Benjamin S. Gelfand, Pierre Kennepohl, Jennifer A. Love

引用次数: 0

Nickel Polyene(yl) Complexes Synthesized from a Dinuclear Ni(I) Compound and (Multi)cyclic Polyenes 由双核镍(I)化合物和（多）环多烯合成的多烯镍(yl)配合物

IF 2.8 3区化学

Organometallics Pub Date : 2024-09-13 DOI: 10.1021/acs.organomet.4c00195

Ben Dong, Zhuo Li, Meng Guo, Yao Qu, Zhenzhou Sun, Li Yang, Rui Liu, Zhixian Xi, Jing Xie, Ji-Hu Su, Biao Wu, Xiao-Juan Yang

{"title":"Nickel Polyene(yl) Complexes Synthesized from a Dinuclear Ni(I) Compound and (Multi)cyclic Polyenes","authors":"Ben Dong, Zhuo Li, Meng Guo, Yao Qu, Zhenzhou Sun, Li Yang, Rui Liu, Zhixian Xi, Jing Xie, Ji-Hu Su, Biao Wu, Xiao-Juan Yang","doi":"10.1021/acs.organomet.4c00195","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00195","url":null,"abstract":"The low-valent Ni–Ni-bonded compound [(NiIL·–)2] (1, L = [(2,6-iPr2C6H3)NC(Me)]2) reacts with a series of multicyclic polyenes through different redox processes, affording seven heteroleptic complexes (2–8) containing nickel, α-diimine L, and polyene (or polyenyl) ligands, where all three components exhibit variable oxidation states. The reaction of 1 with 6-(dimethylamino)fulvene or 6,6-dimethylfulvene led to the reductive dimerization of two fulvene molecules, yielding the dinuclear complexes 2 and 3 with a bridging bis-Cp ligand. In contrast, similar reactions with 6,6-diphenylfulvene or pentamethylcyclopentadiene (C5Me5H) only gave the adducts [LNi(η4-6,6-diphenylfulvene)] (4) or [(L·–)Ni(η4-C5Me5H)] (5) with a neutral polyene molecule. However, the two complexes have different oxidation levels of the nickel center and ligand L, depending on the electronic property of the substrate. By using biphenylene, oxidative addition of a strained C–C bond to nickel occurred to form the biphenyl metallacycle [LNi(μ2-Ph2)] (6). Furthermore, the reaction of 1 with acenaphthylene or C60 afforded complexes [LNi(η2-acenaphthylene)] (7) and [LNi(η2-C60)] (8) featuring an η2-bonded neutral polyene. The results provide evidence of the facile electron transfer between the metal and ligands so that the nickel center can adjust its basicity to coordinate effectively with polyene substrates of different π-acidity.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.8,"publicationDate":"2024-09-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142254673","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

Rhodium-Catalyzed Arene Alkenylation: Selectivity and Reaction Mechanism as a Function of In Situ Oxidant Identity 铑催化的烯炔化反应：选择性和反应机理与原位氧化剂特性的关系

IF 2.5 3区化学

Organometallics Pub Date : 2024-09-12 DOI: 10.1021/acs.organomet.4c0032710.1021/acs.organomet.4c00327

Marc T. Bennett, Kwanwoo A. Park and T. Brent Gunnoe*,

{"title":"Rhodium-Catalyzed Arene Alkenylation: Selectivity and Reaction Mechanism as a Function of In Situ Oxidant Identity","authors":"Marc T. Bennett, Kwanwoo A. Park and T. Brent Gunnoe*, ","doi":"10.1021/acs.organomet.4c0032710.1021/acs.organomet.4c00327","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00327https://doi.org/10.1021/acs.organomet.4c00327","url":null,"abstract":"Rhodium catalyzed arene alkenylation reactions with arenes and olefins using dioxygen as the direct oxidant (e.g., ACS Catal. 2020, 10, 11519), Cu(II) carboxylates (e.g., Science 2015, 348, 421; J. Am. Chem. Soc. 2017, 139, 5474) or Fe(III) carboxylate clusters (e.g., ACS Catal. 2024, 14, 10295), in the presence or absence of dioxygen, have been reported. These processes involve heating catalyst precursor [(η2-C2H4)2Rh(μ-OAc)]2, olefin, arene, and oxidant at temperatures between 120 and 200 °C. Herein, we report comparative studies of Rh-catalyzed arene alkenylation as a function of oxidant identity. This work includes comparisons of catalysis using Cu(II) carboxylates in the presence and absence of dioxygen, catalysis with only dioxygen as the oxidant, and Fe(III) carboxylates in the presence and absence of dioxygen. We report studies of catalysis with each oxidant including reagent concentration dependencies and kinetic isotope effect experiments using C6H6 or C6D6 and protio- or deutero carboxylic acid. Additionally, we probe ortho/meta/para regioselectivity for reactions of ethylene with monosubstituted arenes and Markovnikov/anti-Markovnikov selectivity with monosubstituted olefins. These studies indicate that the variation of oxidant identity impacts catalyst speciation, the reaction mechanism, and the reaction rate. Consequently, distinct Markovnikov/anti-Markovnikov and ortho/meta/para selectivities are observed for catalysis with each oxidant.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.5,"publicationDate":"2024-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.organomet.4c00327","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142276377","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

Bis(benzimidazolin-2-ylidenes): Exploring the Impact of Ligand Properties in the Nickel-Catalyzed Suzuki–Miyaura Coupling 双（苯并咪唑啉-2-亚基）：探索配体性质在镍催化的铃木-宫浦偶联中的影响

IF 2.8 3区化学

Organometallics Pub Date : 2024-09-12 DOI: 10.1021/acs.organomet.4c00138

Claudia S. Zhang, Shreyas Rajesh, Abigail L. Moffett, Timothy H. Chen, Colin D. McMillen, Kerry-Ann Green

{"title":"Bis(benzimidazolin-2-ylidenes): Exploring the Impact of Ligand Properties in the Nickel-Catalyzed Suzuki–Miyaura Coupling","authors":"Claudia S. Zhang, Shreyas Rajesh, Abigail L. Moffett, Timothy H. Chen, Colin D. McMillen, Kerry-Ann Green","doi":"10.1021/acs.organomet.4c00138","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00138","url":null,"abstract":"Bis(benzimidazolin-2-ylidenes) (bisNHCs) are explored as scaffolds for probing the impact of ligand properties in Ni-catalysis. Four well-defined, bench-stable propylene-bridged Ni(II) precatalysts of the type (bisNHC)NiBr2 (3a–3d), with different wingtip groups have been synthesized and evaluated in the Ni-catalyzed Suzuki–Miyaura coupling (SMC). Three new complexes (3b–3d) were characterized by X-ray crystallography. The steric environments of the bisNHC ligands were quantified using the descriptors; buried volume (%VBur) and bite angle. The bisNHC electron-donating abilities were estimated computationally from the absolute minimum molecular electrostatic potential (MESP) at the carbene lone pair (Vmin) and at the carbene nucleus (VC). The bisNHC bearing cyclohexylmethyl wingtip groups exhibits the largest bite angle, highest %VBur, as well as the most negative Vmin and VC values. We established the catalytic competence of all precatalysts for the SMC of aryl sulfamates with arylboronic acids under mild conditions. Precatalyst (3b) bearing cyclohexylmethyl wingtip groups activates rapidly, completely and is consistently the most active. Precatalyst activation studies reveal the formation of Ni(I) species in situ. An independently synthesized model (bisNHC)NiI precatalyst (3e) exhibits comparable catalytic activity to its Ni(II) counterpart (3b). Our findings provide insight into chelating NHCs as robust ligands for stabilizing Ni(I) and Ni(II) species.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.8,"publicationDate":"2024-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142254675","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

Installation of Copper(I) and Silver(I) Sites into TREN-Based Porous Organic Cages via Postsynthetic Metalation 通过后合成金属化将铜（I）和银（I）位点安装到基于 TREN 的多孔有机笼中

IF 2.8 3区化学

Organometallics Pub Date : 2024-09-12 DOI: 10.1021/acs.organomet.4c00247

Hope A. Silva, Bevan S. Whitehead, Christopher D. Hastings, Chandan Kumar Tiwari, William W. Brennessel, Brandon R. Barnett

{"title":"Installation of Copper(I) and Silver(I) Sites into TREN-Based Porous Organic Cages via Postsynthetic Metalation","authors":"Hope A. Silva, Bevan S. Whitehead, Christopher D. Hastings, Chandan Kumar Tiwari, William W. Brennessel, Brandon R. Barnett","doi":"10.1021/acs.organomet.4c00247","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00247","url":null,"abstract":"Porous organic cages (POCs) and metal–organic polyhedra (MOPs) function as zero-dimensional porous materials, able to mimic many functions of insoluble framework materials while offering processability advantages. A popular approach to access tailored metal-based motifs in extended network materials is postsynthetic metalation, which allows metal installation to be decoupled from framework assembly. Surprisingly, this approach has only sparingly been reported for molecular porous materials. In this report, we demonstrate postsynthetic metalation of tetrahedral [4 + 4] POCs assembled from tris(2-aminoethyl)amine (TREN) and 1,3,5-tris(4-formylphenyl)benzene. The trigonally symmetric TREN motif is a common chelator in coordination chemistry and, in the POCs explored herein, readily binds copper(I) and silver(I) to form cationic cages bearing discrete mononuclear coordination fragments. Metalation retains cage porosity, allowing us to compare the sorption properties of the parent organic and metalated cages. Interestingly, introduction of copper(I) facilitates activated oxygen chemisorption, demonstrating how targeted metalation can be exploited to tune the sorption characteristics of porous molecular materials.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.8,"publicationDate":"2024-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142180744","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

Tantalum Catalyzed Hydroaminoalkylation Enables a Telescoping Catalytic Reaction Sequence for the Synthesis of Benzoannulated Indolizidines and Quinolizidines 钽催化加氢氨基烷基化可实现苯并茚并苝和喹嗪并苝合成的催化反应顺序扩展

IF 2.8 3区化学

Organometallics Pub Date : 2024-09-12 DOI: 10.1021/acs.organomet.4c00281

Cameron H. M. Zheng, Carla A. Esslinger, Ole F. Dressler, Rebecca C. DiPucchio, Maria B. Ezhova, Laurel L. Schafer

{"title":"Tantalum Catalyzed Hydroaminoalkylation Enables a Telescoping Catalytic Reaction Sequence for the Synthesis of Benzoannulated Indolizidines and Quinolizidines","authors":"Cameron H. M. Zheng, Carla A. Esslinger, Ole F. Dressler, Rebecca C. DiPucchio, Maria B. Ezhova, Laurel L. Schafer","doi":"10.1021/acs.organomet.4c00281","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00281","url":null,"abstract":"The synthesis of benzoannulated indolizidines and quinolizidines is described through a telescoping reaction sequence featuring hydroaminoalkylation and nickel-catalyzed C–N bond coupling. An in situ generated tantalum (V) ureate catalyst is used to form new Csp3─Csp3 bonds between saturated N-heterocycles and ortho-chlorostyrene enabled by the α C─H bond activation of the amine. The addition of a nickel C─N coupling catalyst generated from Ni(COD)2 and DPPF to the reaction mixture allowed for cyclization. Our method leverages the regiodivergent branched and linear products accessed from N-heterocycle and styrene combinations, which are uniquely achieved by our tantalum catalyst to produce new N-heterocycle framework derivatives. Total isolated overall yields of up to 86% were achieved in a single pot. These advances highlight alternative bond disconnections that enable direct access to distinct new N-heterocycle derivatives through early transition metal catalyzed hydroaminoalkylation.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.8,"publicationDate":"2024-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142180835","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: Ti-Catalyzed “Interrupted” Cascading Hydroamination of 1,6- and 1,7-En-ynes 闪电通讯：钛催化 1,6- 和 1,7- 烯炔的 "间断 "级联加氢反应

IF 2.8 3区化学

Organometallics Pub Date : 2024-09-12 DOI: 10.1021/acs.organomet.4c00354

Kathryn J. Rynders, Daniel N. Huh, Zoe E. Stuart, Zoua Pa Vang, Ian A. Tonks

引用次数: 0

Bis(benzimidazolin-2-ylidenes): Exploring the Impact of Ligand Properties in the Nickel-Catalyzed Suzuki–Miyaura Coupling 双（苯并咪唑啉-2-亚基）：探索配体性质在镍催化的铃木-宫浦偶联中的影响

IF 2.5 3区化学

Organometallics Pub Date : 2024-09-12 DOI: 10.1021/acs.organomet.4c0013810.1021/acs.organomet.4c00138

Claudia S. Zhang, Shreyas Rajesh, Abigail L. Moffett, Timothy H. Chen, Colin D. McMillen and Kerry-Ann Green*,

{"title":"Bis(benzimidazolin-2-ylidenes): Exploring the Impact of Ligand Properties in the Nickel-Catalyzed Suzuki–Miyaura Coupling","authors":"Claudia S. Zhang, Shreyas Rajesh, Abigail L. Moffett, Timothy H. Chen, Colin D. McMillen and Kerry-Ann Green*, ","doi":"10.1021/acs.organomet.4c0013810.1021/acs.organomet.4c00138","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00138https://doi.org/10.1021/acs.organomet.4c00138","url":null,"abstract":"Bis(benzimidazolin-2-ylidenes) (bisNHCs) are explored as scaffolds for probing the impact of ligand properties in Ni-catalysis. Four well-defined, bench-stable propylene-bridged Ni(II) precatalysts of the type (bisNHC)NiBr2 (3a–3d), with different wingtip groups have been synthesized and evaluated in the Ni-catalyzed Suzuki–Miyaura coupling (SMC). Three new complexes (3b–3d) were characterized by X-ray crystallography. The steric environments of the bisNHC ligands were quantified using the descriptors; buried volume (%VBur) and bite angle. The bisNHC electron-donating abilities were estimated computationally from the absolute minimum molecular electrostatic potential (MESP) at the carbene lone pair (Vmin) and at the carbene nucleus (VC). The bisNHC bearing cyclohexylmethyl wingtip groups exhibits the largest bite angle, highest %VBur, as well as the most negative Vmin and VC values. We established the catalytic competence of all precatalysts for the SMC of aryl sulfamates with arylboronic acids under mild conditions. Precatalyst (3b) bearing cyclohexylmethyl wingtip groups activates rapidly, completely and is consistently the most active. Precatalyst activation studies reveal the formation of Ni(I) species in situ. An independently synthesized model (bisNHC)NiI precatalyst (3e) exhibits comparable catalytic activity to its Ni(II) counterpart (3b). Our findings provide insight into chelating NHCs as robust ligands for stabilizing Ni(I) and Ni(II) species.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.5,"publicationDate":"2024-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.organomet.4c00138","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142276330","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

Cobalt-Complexed Acetylenic Tetrads, a Molecular Scaffold for Quadruple Ionic Functionalization Reactions 钴络合乙酰四烯，四重离子官能团化反应的分子支架

IF 2.8 3区化学

Organometallics Pub Date : 2024-09-12 DOI: 10.1021/acs.organomet.4c00088

Gagik G. Melikyan, Nicole Babayans, Natalie Kalpakyan, Claire Herrera, Pavel Rublev, Nikolay V. Tkachenko, Alexander I. Boldyrev

{"title":"Cobalt-Complexed Acetylenic Tetrads, a Molecular Scaffold for Quadruple Ionic Functionalization Reactions","authors":"Gagik G. Melikyan, Nicole Babayans, Natalie Kalpakyan, Claire Herrera, Pavel Rublev, Nikolay V. Tkachenko, Alexander I. Boldyrev","doi":"10.1021/acs.organomet.4c00088","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00088","url":null,"abstract":"A methodology was developed for introducing nucleophiles into the α- and α′-positions of the dicobalt hexacarbonyl-complexed acetylenic tetrads. A synthetic algorithm included the entry of a given nucleophile to both termini of the acetylenic tetrad A (α-Nu1-α′-Nu1; α-Nu2-α′-Nu2), or a pair of select nucleophiles arranged unsymmetrically in opposing sequences (α-Nu1-α′-Nu2; α-Nu2-α′-Nu1). Thus, every substrate A and a pair of C-nucleophiles give rise to an organometallic rectangle (B-E) and synthetic octagon (B-I). The site-selective transformations that exploited the difference in thermodynamic stabilities of the α- and α′-cationoids, and thus in heterolytic bond dissociation energies (BDE) values, were coined the “quadruple ionic functionalization reactions.” The substrate and reagent bases were expanded to include aromatic carbo- and heterocycles as α-substituents, and aliphatic and aromatic reagents as nucleophiles. Density functional theory calculations allowed for identifying qualitative descriptors that explained the preponderant bond formation in more stabilized, albeit more hindered α-propargyl positions. In mechanistic terms, reactions at the competing sites (α- vs α-′) occupy distinctly different positions in the mechanistic continuum spanning the classical SN1 and SN2 processes. Overall, quadruple functionalization methodology allows for the practically limitless expansion of the acetylenic tetrads and a nucleophile base, and the completion of a multitude of organometallic rectangles and synthetic octagons.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.8,"publicationDate":"2024-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142180834","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