Organometallics最新文献_第3页

Reactivity of [TismPriBenz]MgH and [TismPriBenz]MgMe Towards Esters: Alkoxide Elimination and C–C Bond Formation [TismPriBenz]MgH和[TismPriBenz]MgMe对酯的反应性：醇酮消除和C-C键形成

IF 2.9 3区化学

Organometallics Pub Date : 2025-08-26 DOI: 10.1021/acs.organomet.5c00190

David A. Vaccaro, Ran Yan and Gerard Parkin*,

{"title":"Reactivity of [TismPriBenz]MgH and [TismPriBenz]MgMe Towards Esters: Alkoxide Elimination and C–C Bond Formation","authors":"David A. Vaccaro, Ran Yan and Gerard Parkin*, ","doi":"10.1021/acs.organomet.5c00190","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00190","url":null,"abstract":"The reactivity of Mg–H and Mg–Me bonds of [TismPriBenz]MgH and [TismPriBenz]MgMe towards esters reveals additional pathways to those that have been observed for aldehydes and ketones, namely insertion and enolate formation. For example, [TismPriBenz]MgH and [TismPriBenz]MgMe react with the formate ester HCO2Me to afford the methoxy derivative, [TismPriBenz]MgOMe, via a process that is proposed to involve β-methoxide elimination from a [TismPriBenz]MgOCH(X)OMe intermediate (X = H, Me). Likewise, [TismPriBenz]MgH reacts with the acetate ester, MeCO2Et, to afford the ethoxide complex, [TismPriBenz]MgOEt. In contrast, while the methyl complex [TismPriBenz]MgMe likewise reacts with MeCO2Et to form [TismPriBenz]MgOEt, the β-keto ester enolate derivative, [TismPriBenz]Mg(κ2-etac) [κ2-etac = MeC(O)CHC(O)OEt], is also obtained via a reaction that involves the formation of a C–C bond. The latter compound is additionally obtained by the reaction of [TismPriBenz]MgMe with ethyl acetoacetate, MeC(O)CH2C(O)OEt, presumably via a reaction with the enol tautomer, MeC(OH)CHC(O)OEt. [TismPriBenz]MgOMe and [TismPriBenz]Mg(κ2-etac) have been structurally characterized by X-ray diffraction.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 17","pages":"1893–1905"},"PeriodicalIF":2.9,"publicationDate":"2025-08-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145007391","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

The Role of Substrate Acidity in PN3P–Ru Pincer Complex Catalyzed Formic Acid Dehydrogenation: Pseudo-Dearomatization vs Non-Dearomatization Pathways 底物酸度在PN3P-Ru钳形配合物催化甲酸脱氢中的作用：伪脱芳与非脱芳途径

IF 2.9 3区化学

Organometallics Pub Date : 2025-08-25 DOI: 10.1021/acs.organomet.5c00244

Manjaly J. Ajitha*, and , Kuo-Wei Huang*,

{"title":"The Role of Substrate Acidity in PN3P–Ru Pincer Complex Catalyzed Formic Acid Dehydrogenation: Pseudo-Dearomatization vs Non-Dearomatization Pathways","authors":"Manjaly J. Ajitha*,  and , Kuo-Wei Huang*, ","doi":"10.1021/acs.organomet.5c00244","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00244","url":null,"abstract":"Metal–ligand cooperation (MLC) plays a crucial role in catalysis by enabling substrate activation through coordinated interactions between the metal center and ligand framework. To elucidate the mechanism for the PN3P–Ru-pincer complex catalyzed formic acid (HCOOH) dehydrogenation (FADH) reaction, pseudo-dearomatization and non-dearomatization pathways were investigated. HCOOH acidity is a key determinant with acid–base interactions favoring a non-dearomatization pathway. The base, triethylamine (Et3N), facilitates the formate ion generation, followed by the catalyst activation. Stability analysis indicates that the five-coordinated Ru species with a Cl– counterion is the most stable form in solution compared to its six-coordinated species. Under FADH conditions, decarboxylation is identified as the rate-determining step (RDS), consistent with experimental kinetic isotope effect (KIE) observations. Although the dearomatized PN3P–Ru pincer complex can be synthesized under basic conditions without HCOOH, it rapidly rearomatizes in the presence of HCOOH and remains in its aromatic form throughout the catalytic cycle. Our findings suggest that dearomatization/rearomatization may not be essential for these pincer systems. These insights refine our understanding of the aromatization/dearomatization-based MLC in homogeneous FADH reactions catalyzed by the PN3P–Ru pincer complexes and provide guiding principles for the development of next-generation catalysts for energy-related transformations.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 18","pages":"2099–2106"},"PeriodicalIF":2.9,"publicationDate":"2025-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145104051","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

Efficient Ring Closing Metathesis by NHC-Supported (Arylimido)vanadium(V)-Alkylidene Catalysts Containing Perhalophenoxide Ligands: Exclusive RCM under High Substrate Concentration 含过卤代酚配体的nhc负载（芳基氨基）钒(V)-烷基基催化剂的高效合环复合反应：高底物浓度下的独占RCM

IF 2.9 3区化学

Organometallics Pub Date : 2025-08-21 DOI: 10.1021/acs.organomet.5c00224

Jirapa Suthala, Moe Unoki, Michael R. Buchmeiser* and Kotohiro Nomura*,

{"title":"Efficient Ring Closing Metathesis by NHC-Supported (Arylimido)vanadium(V)-Alkylidene Catalysts Containing Perhalophenoxide Ligands: Exclusive RCM under High Substrate Concentration","authors":"Jirapa Suthala, Moe Unoki, Michael R. Buchmeiser* and Kotohiro Nomura*, ","doi":"10.1021/acs.organomet.5c00224","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00224","url":null,"abstract":"Ring closing metathesis (RCM) reactions of N,N-diallyl-4-toluenesulfonamide (S1) and N,N-diallylaniline (S2) by V(N-2,6-Cl2C6H3)(CHSiMe3)(OC6X5)(NHC) [X = F, Cl (4), Br (5); NHC = 1,3-bis(2,6-dimethylphenyl)imidazole-2-ylidene (IXy)] exclusively afforded the corresponding ring closed products (yields 83 to >99%) under high initial substrate concentration conditions (3.2–24 M). A significant increase in the activity was observed upon increasing the substrate concentrations, leading to highly efficient RCM [RCM of S2 by 4,5: TON = >1000, TOF = >100 s–1, yield (conv.) 95 to >99%]. The RCM of diallyl ether and diallyl thioether afforded the corresponding ring closed products exclusively, whereas the activities increased with dilution of the substrate concentrations. The RCM of 1,7-octadiene also gave cyclohexene.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 17","pages":"1870–1875"},"PeriodicalIF":2.9,"publicationDate":"2025-08-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.organomet.5c00224","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145007368","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

Correlating the TMA Content with Structural Evolution and Catalytic Behavior of dMAO in Ethylene Polymerization 乙烯聚合中TMA含量与dMAO结构演化及催化行为的关系

IF 2.9 3区化学

Organometallics Pub Date : 2025-08-21 DOI: 10.1021/acs.organomet.5c00254

Yanjiao Xu, Jie Hu, Xuxin Zhu, Shuying Xie, Haomiao Zhang*, Jingdai Wang and Yongrong Yang,

{"title":"Correlating the TMA Content with Structural Evolution and Catalytic Behavior of dMAO in Ethylene Polymerization","authors":"Yanjiao Xu, Jie Hu, Xuxin Zhu, Shuying Xie, Haomiao Zhang*, Jingdai Wang and Yongrong Yang, ","doi":"10.1021/acs.organomet.5c00254","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00254","url":null,"abstract":"Methylaluminoxane (MAO) and trimethylaluminum (TMA) are essential cocatalysts in olefin polymerization and oligomerization, yet their interplay and impact on catalytic performance remain incompletely understood. In this study, TMA-depleted MAO (dMAO) was obtained via vacuum drying and redissolved, followed by controlled reintroduction of TMA to investigate its structural and catalytic effects. Diffusion-ordered NMR spectroscopy (DOSY) revealed that untreated MAO exhibits a broad oligomeric size distribution (5.99–10.4 Å) in toluene. Vacuum drying removes free and loosely bound TMA, yielding more uniform MAO clusters (9.10 Å). Catalytic studies demonstrate that in Cp2ZrCl2-catalyzed ethylene polymerization, TMA acts as a chain-transfer agent, with optimal activity at a TMA/dMAO ratio of 1:3. In Fe(acac)3-catalyzed oligomerization, moderate TMA levels enhance α-olefin selectivity (up to 90%) and suppress wax formation. Similarly, in Cr/PNP-catalyzed tetramerization, TMA improves 1-octene selectivity to 77.1% while minimizing PE byproducts. These findings underscore the importance of TMA control in optimizing the MAO structure and catalytic efficiency for polyolefin production.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 17","pages":"1977–1986"},"PeriodicalIF":2.9,"publicationDate":"2025-08-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145007369","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: Bismuthinidenes as Lewis Bases in Reversible C(sp3)–O Bond Cleavage 闪光通讯：铋在可逆C(sp3) -O键裂解中的路易斯碱作用

IF 2.9 3区化学

Organometallics Pub Date : 2025-08-20 DOI: 10.1021/acs.organomet.5c00260

Davide Spinnato, Hye Won Moon, Markus Leutzsch, Nils Nöthling and Josep Cornella*,

引用次数: 0

Cis-1,4-Enhanced Polymerization of Isoprene Catalyzed by Iminopyridine-Iron(II) Complexes 亚氨基吡啶-铁（II）配合物催化顺式-1,4增强异戊二烯聚合

IF 2.9 3区化学

Organometallics Pub Date : 2025-08-20 DOI: 10.1021/acs.organomet.5c00210

Xiaoyu Chen, Guang-Yu Zhu*, Guangqiang Xu, Liang Wang* and Qinggang Wang*,

{"title":"Cis-1,4-Enhanced Polymerization of Isoprene Catalyzed by Iminopyridine-Iron(II) Complexes","authors":"Xiaoyu Chen, Guang-Yu Zhu*, Guangqiang Xu, Liang Wang* and Qinggang Wang*, ","doi":"10.1021/acs.organomet.5c00210","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00210","url":null,"abstract":"(Imino)pyridine late transition-metal complexes have been well-explored in olefin polymerization. Among them, iron-based (imino)pyridine complexes stand out due to their abundance, low toxicity, and versatility in conjugated diene polymerization. While ligand modifications have predominantly focused on Nimine-substituents, direct pyridine ring functionalization remains underexplored despite emerging evidence of its potential influence. This study introduces a family of 6-methoxy-substituted (imino)pyridine iron catalysts for isoprene polymerization with high cis-1,4 selectivity (up to 91%). Unlike conventional isolated modification strategies that use steric hindrance substituents of Nimine, this work highlights the necessity of considering the ligand framework as an integrated system where interactions between distinct structural units govern polymerization behavior. These well-defined iron complexes challenge prior assumptions that pyridine ring modifications lack utility in conjugated diene polymerization and redefine future approaches to ligand optimization by emphasizing holistic over isolated structural adjustments in (imino)pyridine late transition-metal complexes.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 17","pages":"1937–1944"},"PeriodicalIF":2.9,"publicationDate":"2025-08-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145007372","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 and Single-Crystal X-ray Structures of Sterically Hindered Three Half-Sandwich (η6-p-Cymene)ruthenium(II) Schiff Base Complexes: Catalytic Applications in Selective Monoalkylation of Amines and Synthesis of Amides 位阻三半夹心（氮- 6-对伞花烃）钌（II）席夫碱配合物的合成及单晶x射线结构：在胺选择性单烷基化和酰胺合成中的催化应用

IF 2.9 3区化学

Organometallics Pub Date : 2025-08-20 DOI: 10.1021/acs.organomet.5c00221

Bhumika Agrahari, Samaresh Layek, Rakesh Ganguly and Devendra Deo Pathak*,

{"title":"Synthesis and Single-Crystal X-ray Structures of Sterically Hindered Three Half-Sandwich (η6-p-Cymene)ruthenium(II) Schiff Base Complexes: Catalytic Applications in Selective Monoalkylation of Amines and Synthesis of Amides","authors":"Bhumika Agrahari, Samaresh Layek, Rakesh Ganguly and Devendra Deo Pathak*, ","doi":"10.1021/acs.organomet.5c00221","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00221","url":null,"abstract":"Abstract Transition metal complex-mediated organic synthesis is a fascinating area of mutual interest to both organic and inorganic chemists. In this work, three new bulky half-sandwich ruthenium(II) Schiff base complexes of the general formula [(p-cymene)L1RuCl] Ru1, [(p-cymene)L2RuCl] Ru2, and [(p-cymene)L3RuCl]OTf Ru3 [HL1 = 2-(2,6-dibenzhydryl-4-methylphenyliminomethyl)phenol, HL2 = 2-(2,6-dibenzhydryl-4-methylphenyliminomethyl-5-pentan-3-yl)phenol, L3= 2,6-dibenzhydryl-N-(isoquinolin-1-ylmethylene)-4-methylaniline] were synthesized by the reaction of precursor complex [(p-cymene)RuCl2]2 with the corresponding Schiff base ligands and isolated as colored crystalline solids in high yields (85–87%). All Schiff base ligands and half-sandwich ruthenium complexes were characterized by ESI-MS, FT-IR and 1H and 13C{1H} NMR. The ligands (HL2 and L3) and complexes (Ru1–Ru3) were structurally characterized by single-crystal X-ray diffraction studies. The single-crystal X-ray structures of the complexes (Ru1–Ru3) confirmed a pseudo-octahedral half-sandwich piano-stool geometry around ruthenium. The complexes were found to be efficient catalysts for selective monoalkylation of primary amines via the hydrogen borrowing strategy and synthesis of a series of amides from various aldehyde and hydroxylamine hydrochloride. Among all three complexes, the cationic complex (Ru3) exhibited the best catalytic activity than the neutral analogues Ru1 and Ru2 in both the reactions. The synthesized organic products were characterized by 1H and 13C{1H} NMR analysis.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 17","pages":"1951–1964"},"PeriodicalIF":2.9,"publicationDate":"2025-08-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145007454","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

Thionitrosyl Complexes of Technetium and Rhenium with Sterically Encumbered m-Terphenyl Isocyanides─Steric Bulk Matters 空间负载间terphenyl异氰酸酯与锝、铼的硫代硝基配合物─空间块体物质

IF 2.9 3区化学

Organometallics Pub Date : 2025-08-19 DOI: 10.1021/acs.organomet.5c00250

Domenik Nowak, Guilhem Claude, Anna-Maria Tsirigoni, Adelheid Hagenbach, Joshua S. Figueroa* and Ulrich Abram*,

{"title":"Thionitrosyl Complexes of Technetium and Rhenium with Sterically Encumbered m-Terphenyl Isocyanides─Steric Bulk Matters","authors":"Domenik Nowak, Guilhem Claude, Anna-Maria Tsirigoni, Adelheid Hagenbach, Joshua S. Figueroa* and Ulrich Abram*, ","doi":"10.1021/acs.organomet.5c00250","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00250","url":null,"abstract":"Low-valent thionitrosyl complexes of technetium and rhenium with the bulky isocyanides CNArTripp2, CNArDipp2, and CNArMes2 (Tripp = 2,4,6-triisopropylphenyl, Dipp = 2,6-diisopropylphenyl, Mes = 2,4,6-trimethylphenyl) have been synthesized by reactions of the corresponding nitridotechnetium(V) or rhenium(V) compounds with disulfur dichloride. The structures of the products and the oxidation states of the resulting metal ions are mainly controlled by the steric bulk of the terphenyl isocyanide ligands. Bis(isocyanide) Tc(II) and Re(II) were obtained exclusively with CNArTripp2 or CNArDipp2, which is in contrast with the more diverse reaction outcomes with the less bulky CNArMes2, where the products also include metal(I) and dimeric compounds. The obtained complexes [ReVNCl2(CNArTripp2)2(MeOH)], [ReVNCl2(CNArDipp2)2], [ReVNCl2(CNArMes2)3], [TcVNCl2(CNArTripp2)2], [ReII(NS)Cl3(CNArTripp2)2], [ReII(NS)Cl3(CNArDipp2)2], [ReI(NS)Cl2(CNArMes2)3], [TcII(NS)Cl3(CNArTripp2)2], [TcII(NS)Cl3(CNArDipp2)2], [TcII(NS)Cl2(CNArMes2)3]Cl, and [{Tc(NS)Cl(CNArMes2)2}2Cl2] were studied spectroscopically and partially by X-ray diffraction.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 17","pages":"1965–1976"},"PeriodicalIF":2.9,"publicationDate":"2025-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.organomet.5c00250","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145007447","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

Flash Communication: An ortho-Trifluoromethylphenyl Substituted Phosphine Ligand for Applications in Gold(I) Catalysis 闪光通信：邻三氟甲基苯基取代膦配体在金催化中的应用(I)

IF 2.9 3区化学

Organometallics Pub Date : 2025-08-18 DOI: 10.1021/acs.organomet.5c00240

Itxaso Bustos, Nil Roig and Adrian B. Chaplin*,

引用次数: 0

Hafnium-Catalyzed Controlled Polymerization of 1,5-Hexadiene toward Polyolefin-Based Graft Copolymers for Poly(lactic Acid) Toughening with High Transparency 铪催化1,5-己二烯调控聚合制备高透明聚乳酸接枝共聚物

IF 2.9 3区化学

Organometallics Pub Date : 2025-08-15 DOI: 10.1021/acs.organomet.5c00213

Yingxia Han, Mengnan Li, Shaofeng Liu* and Zhibo Li,

{"title":"Hafnium-Catalyzed Controlled Polymerization of 1,5-Hexadiene toward Polyolefin-Based Graft Copolymers for Poly(lactic Acid) Toughening with High Transparency","authors":"Yingxia Han, Mengnan Li, Shaofeng Liu* and Zhibo Li, ","doi":"10.1021/acs.organomet.5c00213","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00213","url":null,"abstract":"This study developed an efficient strategy based on hafnium catalysts for the synthesis of poly(lactic acid) (PLLA) toughening agents. The homopolymerization of 1,5-hexadiene (HD) catalyzed by selected hafnium complexes successfully prepared poly(1,5-hexadiene) (PHD) with reactive C═C double bonds in the side chains (up to 11 mol %), and the catalytic activity was as high as 106 g(polymer)·mol–1(Hf)·h–1. Hydroxylated PHDs (PHDOH) were obtained by functionalizing the PHD with β-mercaptoethanol using thiol–ene click chemistry. Subsequently, a series of graft copolymers (PHD-g-PLLAs) with different PLLA side chain lengths was synthesized from ring-opening polymerization of l-lactide (l-LA) with PHDOH as the macromolecule initiator and cyclic trimeric phosphazene base as the organocatalyst. The graft copolymer, as an efficient toughening agent, can significantly enhance the toughness of commercial PLLA, showing a maximum elongation at break of up to 183%, which is approximately 30-fold that of neat PLLA. Meanwhile, the resultant toughened commercial PLLA maintained high transparency and rigidity. This method provides a promising approach for the development of PLLA materials with both excellent toughness and optical transparency.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 17","pages":"1926–1936"},"PeriodicalIF":2.9,"publicationDate":"2025-08-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145007418","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