Organometallics最新文献_第4页

A Zincke-Inspired Cycloreversion/Cyclization Sequence with Arrested Rearomatization: Synthesis of 2-Aminodihydropyridinium Complexes 一种锌激发的环还原/环化序列与阻滞重芳构化：2-氨基二氢吡啶配合物的合成

IF 2.9 3区化学

Organometallics Pub Date : 2025-08-15 DOI: 10.1021/acs.organomet.5c00199

Jonathan D. Dabbs, Caleb C. Taylor, Benjamin F. Livaudais, Alvin Q. Meng, Brian T. Quillin, Diane A. Dickie and W. Dean Harman*,

{"title":"A Zincke-Inspired Cycloreversion/Cyclization Sequence with Arrested Rearomatization: Synthesis of 2-Aminodihydropyridinium Complexes","authors":"Jonathan D. Dabbs, Caleb C. Taylor, Benjamin F. Livaudais, Alvin Q. Meng, Brian T. Quillin, Diane A. Dickie and W. Dean Harman*, ","doi":"10.1021/acs.organomet.5c00199","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00199","url":null,"abstract":"The Zincke reaction combines a pyridinium salt bearing an N-withdrawing group and a primary aliphatic amine to form an alkylated pyridinium salt through a ring-opening/ring-closing sequence. Herein, we explore the analogous reaction sequence for a pyridinium salt η2-bound to a transition metal. We find that the N-sulfonylated pyridinium ligand (pyR1, where R1 = mesyl or tosyl) of [WTp(NO)(PMe3)(η2-pyR1)]OTf selectively reacts with a primary amine, and the resulting 2-aminodihydropyridine complex then undergoes a tungsten-stabilized ring-scission to form the corresponding η2-azatriene complex. Subsequent ring-closure between the newly installed amine and the sulfonylated imine results in a new aminodihydropyridinium species. This dihydropyridinium resists rearomatization due to a stabilizing influence of the tungsten fragment. Subsequent displacement of the sulfonamide by pendent heteroatoms leads to the formation of new heterocyclic frameworks. Herein the syntheses of 30 heterocyclic complexes are described (3 characterized by SC-XRD) including 7 examples of multicyclic systems.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 17","pages":"1920–1925"},"PeriodicalIF":2.9,"publicationDate":"2025-08-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.organomet.5c00199","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145007403","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

THF Activation from the Synthesis of Reactive Uranium(III)-Pnictogen Bonds 反应性铀(III)- pnicgen键合成的THF活化

IF 2.9 3区化学

Organometallics Pub Date : 2025-08-13 DOI: 10.1021/acs.organomet.5c00215

Lauren M. Lopez, Diana Perales, Caleb J. Tatebe, Michaela R. Bronstetter, Matthias Zeller and Suzanne C. Bart*,

引用次数: 0

A DFT Study of the Hydroacylation Reaction Catalyzed by Rhodium Complexes with Small-Bite-Angle Diphosphine Ligands: The Crucial Role of External Lewis Bases 小咬角二膦配体铑配合物催化氢酰化反应的DFT研究：外路易斯碱的关键作用

IF 2.9 3区化学

Organometallics Pub Date : 2025-08-12 DOI: 10.1021/acs.organomet.5c00179

Andrew S. Weller, Michael C. Willis, Libero J. Bartolotti, Andrew T. Morehead Jr.* and Andrew L. Sargent*,

引用次数: 0

Synthesis of a Well-Defined Conjugated Polymer Via Nickel-Catalyzed Direct Arylation Polymerization (Ni-DArP) 镍催化直接芳基化聚合合成一种定义良好的共轭聚合物（Ni-DArP）

IF 2.9 3区化学

Organometallics Pub Date : 2025-08-12 DOI: 10.1021/acs.organomet.5c00201

Grace E. Castillo, and , Barry C. Thompson*,

{"title":"Synthesis of a Well-Defined Conjugated Polymer Via Nickel-Catalyzed Direct Arylation Polymerization (Ni-DArP)","authors":"Grace E. Castillo,  and , Barry C. Thompson*, ","doi":"10.1021/acs.organomet.5c00201","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00201","url":null,"abstract":"Direct arylation polymerization (DArP) is a sustainable method of conjugated polymer synthesis; however, expensive and low-abundance palladium catalysts are nearly ubiquitous in this chemistry. Catalysts based on earth-abundant first-row transition metals are little-explored but would represent a significant improvement in the sustainability of DArP and potentially enable new reactivity. Beyond previously explored copper catalysts, nickel catalysts offer access to possibly more effective polymerization chemistry. Previous reports of DArP using a Ni catalyst yielded cross-linked, insoluble materials. Here we report the first instance of a linear, well-defined conjugated polymer synthesized using Ni-catalyzed DArP (Ni-DArP) where 5,5′-(2,5-bis(hexyloxy)-1,4-phenylene)dithiazole was copolymerized with 1,4-dibromo-2,5-bis((2-ethylhexyl)oxy)benzene using Ni(OAc)2. Polymerizations proceeded at catalyst loadings of 5–20 mol % affording polymers with molar masses up to 10.2 kg/mol and yields up to 55%, on-par with Cu-DArP. The stable, commercial species Ni(OAc)2·4H2O can be easily dehydrated to yield the active catalyst. Regioselectivity for the 2-position of thiazole with both Ni and Cu was observed, contrasting selectivity for the 5-position with Pd, demonstrated in both polymerizations and small-molecule couplings, along with the Ni-catalyzed conditions potentially favoring ring walking relative to that of Cu. The complementary nature of the catalysts demonstrates the value of developing earth-abundant catalysts for DArP beyond the relevance to sustainability.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 16","pages":"1729–1734"},"PeriodicalIF":2.9,"publicationDate":"2025-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144892528","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

(κ3-N∩N∩N)-Palladium Pincer Complex-Catalyzed Synthesis of Quinazolin-4(3H)-Ones Through the Acceptorless Dehydrogenation Process: Experimental Results and Computational Insights （κ3-N∩N∩N）-钯钳形配合物催化无受体脱氢合成喹唑啉-4(3H)- 1：实验结果与计算见解

IF 2.9 3区化学

Organometallics Pub Date : 2025-08-11 DOI: 10.1021/acs.organomet.5c00125

Selvam Sivaprakash, Srilata Goswami, Hemalatha Maricherla, Mahesh Kumar Ravva, Dinesh Harijan, Ganesan Prabusankar, Arlin Jose Amali* and Devarajan Suresh*,

{"title":"(κ3-N∩N∩N)-Palladium Pincer Complex-Catalyzed Synthesis of Quinazolin-4(3H)-Ones Through the Acceptorless Dehydrogenation Process: Experimental Results and Computational Insights","authors":"Selvam Sivaprakash, Srilata Goswami, Hemalatha Maricherla, Mahesh Kumar Ravva, Dinesh Harijan, Ganesan Prabusankar, Arlin Jose Amali* and Devarajan Suresh*, ","doi":"10.1021/acs.organomet.5c00125","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00125","url":null,"abstract":"In this work, the synthesis of the palladium complexes coordinated with thiazoline-derived N∩NH∩N pincer ligands and their application in the synthesis of quinazolin-4(3H)-ones through the acceptorless dehydrogenation (ADH) process along with the sequential C–C coupling reaction is presented. Initially, treatment of chloroacetyl chloride with thiazoline amine produced compound N∩NH∩CH2Cl (2), which on subsequent reaction with morpholine or piperidine afforded the corresponding N∩NH∩N pincer ligands 3 and 4. Reactions of ligands with PdCl2 or Pd(OAc)2 in a 1:1 molar ratio at room temperature afforded the mononuclear palladium(II) complexes [(κ3-N∩N∩N)PdX] (X = Cl, OAc) 5–8, while treatment of ligands with Pd(OAc)2 in the presence of trifluoroacetic acid afforded the complexes [(κ3-N∩N∩N)Pd(TFA)] 9 and 10. 1H, 13C{1H} NMR spectroscopic techniques and HR-MS data confirm the proposed structures and chemical compositions. Further, molecular structures of 3, 4, 6, 8, and 10 were established through single-crystal X-ray diffraction studies. The catalytic activity of palladium(II) complexes 5–10 was evaluated for the synthesis of quinazolinone derivatives from 2-aminobenzamide and substituted benzyl alcohols via ADH coupling reactions along with sequential C–C coupling reactions. The thermodynamics associated with this transformation have been established using DFT calculations.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 16","pages":"1780–1793"},"PeriodicalIF":2.9,"publicationDate":"2025-08-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144892597","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: An Inorganic Version of Alkyne–Azide Cycloaddition: Click-Like Reactions of an o-Carboranyl Iminoborane with Organic Azides 闪光通讯：一种无机版本的炔叠氮化物环加成：o-碳硼基亚硼烷与有机叠氮化物的点击式反应

IF 2.9 3区化学

Organometallics Pub Date : 2025-08-11 DOI: 10.1021/acs.organomet.5c00243

Libo Xiang, Andrea Gisbert Albacar, Junyi Wang, Alexander Matler, Tobias Preitschopf, Maik Finze and Qing Ye*,

{"title":"Flash Communication: An Inorganic Version of Alkyne–Azide Cycloaddition: Click-Like Reactions of an o-Carboranyl Iminoborane with Organic Azides","authors":"Libo Xiang, Andrea Gisbert Albacar, Junyi Wang, Alexander Matler, Tobias Preitschopf, Maik Finze and Qing Ye*, ","doi":"10.1021/acs.organomet.5c00243","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00243","url":null,"abstract":"The concept of inorganic-alkyne-based click (iaclick) was introduced. Analogous to the azide–alkyne cycloaddition, o-carboranyl iminoborane 1, an inorganic alkyne, readily underwent cycloaddition with a variety of azides at room temperature and under catalyst-free conditions. This offered a modular synthetic approach to o-carboranyl tetrazaboroles 2a–2h in excellent yields. Stability tests of 2a–2h were performed. These compounds displayed considerable thermal stability, with decomposition temperatures in the range of 195.0–270.8 °C, determined by STA. Air stability tests in the solid state showed that the 1-alkyl derivatives were stable for hours, while the 1-aryl derivatives were stable for weeks. Therefore, upon straightforward incorporation of o-carborane units into organic frameworks, iaclick strategy opens a new avenue for the construction of stable o-carborane-based functional molecules with potential for diverse applications.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 16","pages":"1756–1759"},"PeriodicalIF":2.9,"publicationDate":"2025-08-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144892664","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

IPr**(4-Bp)─Highly Hindered, Ring Extended N-Heterocyclic Carbenes IPr**(4-Bp)──高阻碍、扩展环的n -杂环碳烯

IF 2.9 3区化学

Organometallics Pub Date : 2025-08-07 DOI: 10.1021/acs.organomet.5c00232

Yuzhuo Sha, Wenchao Chu*, Roger Lalancette, Roman Szostak and Michal Szostak*,

{"title":"IPr**(4-Bp)─Highly Hindered, Ring Extended N-Heterocyclic Carbenes","authors":"Yuzhuo Sha, Wenchao Chu*, Roger Lalancette, Roman Szostak and Michal Szostak*, ","doi":"10.1021/acs.organomet.5c00232","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00232","url":null,"abstract":"There is a strong demand for the development of sterically hindered N-heterocyclic carbenes due to their potential to stabilize reactive organometallic species. IPr* (IPr* = 1,3-bis(2,6-bis(diphenylmethyl)-4-methylphenyl)imidazo-2-ylidene) is a highly hindered and sterically flexible ligand, which has found broad utilization in coordination chemistry. Herein, we report the synthesis, structural, and electronic characterization of IPr**(4-Bp)─a class of novel, sterically bulky, and easily accessible N-heterocyclic carbene ligands that bear biphenyl wingtips. Coordination chemistry to Ag(I), Cu(I), and Pd(II) is presented. The biphenyl wingtip permits extension of the %Vbur of IPr**(4-Bp) to 58.8%, linear geometry, which is the highest reported to date for imidazol-2-ylidene ligands. The synthesis of an electron-rich congener, IPr**MeO(4-Bp), which is analogous to the popular IPr*MeO ligand, is also presented. Coordination to Pd(II) demonstrates steric flexibility, where the %Vbur changes to 42.8% for square planar geometry. The study demonstrates that IPr**(4-Bp) with an extended biphenyl wingtip is sterically bulkier than common imidazol-2-ylidenes, including IPr, IPr*, IPr#, and IPr*(2-Np). Considering the essential role of sterically hindered N-heterocyclic carbene ligands in various areas of coordination chemistry and metal catalysis, this new class of NHCs is poised for rapid and widespread application.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 16","pages":"1848–1853"},"PeriodicalIF":2.9,"publicationDate":"2025-08-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.organomet.5c00232","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144892614","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

Employing a Two-Step Carbonylation and Condensation Approach to Expand the Scope of Hydroesterificative Polymerization 采用两步羰基化缩合法扩大氢酯化聚合的范围

IF 2.9 3区化学

Organometallics Pub Date : 2025-08-07 DOI: 10.1021/acs.organomet.5c00207

Ryan J. Anderson, Janaya D. Sachs and Ian A. Tonks*,

引用次数: 0

Leveraging Ligand Cooperativity to Accelerate C–H Activation of Alkynes Using a Tris(amido) Zirconium Complex 利用三（氨基）锆配合物利用配体协同性加速炔的碳氢活化

IF 2.9 3区化学

Organometallics Pub Date : 2025-08-06 DOI: 10.1021/acs.organomet.5c00225

Nicholas A. Garcia, George M. Hernandez and Courtney C. Roberts*,

引用次数: 0

Examination of Dianionic Diamide Ligand Structural Effects on Ti-Catalyzed Hydrohydrazination of Terminal Alkynes 双阴离子二胺配体对钛催化末端炔氢肼化反应的结构影响研究