Organometallics最新文献_第10页

Branched Polyethylene Synthesized by Salicylaldiminato Nickel Complexes with an Ethereal Donor Group 含空灵给基的水杨醛缩镍配合物合成支化聚乙烯

IF 2.5 3区化学

Organometallics Pub Date : 2025-05-19 DOI: 10.1021/acs.organomet.5c0001810.1021/acs.organomet.5c00018

Yi Wu, Inzamam Abbasi, Chenggong Sang, Dongcai Shen, Renrong Liu* and Wenjie Tao*,

引用次数: 0

Mechanistic Organometallic Studies Drive Reagent Selection and Catalyst Design for the Palladium-Catalyzed Trifluoromethylthiolation of Aryl Electrophiles 有机金属机制研究驱动钯催化芳基亲电试剂三氟甲基硫基化的试剂选择和催化剂设计

IF 2.5 3区化学

Organometallics Pub Date : 2025-05-19 DOI: 10.1021/acs.organomet.5c0014810.1021/acs.organomet.5c00148

Joshua Thedford, and , Melanie S. Sanford*,

{"title":"Mechanistic Organometallic Studies Drive Reagent Selection and Catalyst Design for the Palladium-Catalyzed Trifluoromethylthiolation of Aryl Electrophiles","authors":"Joshua Thedford,  and , Melanie S. Sanford*, ","doi":"10.1021/acs.organomet.5c0014810.1021/acs.organomet.5c00148","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00148https://doi.org/10.1021/acs.organomet.5c00148","url":null,"abstract":"This article describes a detailed investigation of the palladium-catalyzed coupling of aryl (pseudo)halides (ArX) with MSCF3 to form aryl trifluoromethylthioethers (ArSCF3). Mechanistic organometallic studies are used to interrogate two key elementary steps of the catalytic cycle: (1) transmetalation of PdII(Ar)(X) complexes with MSCF3 and (2) Ar–SCF3 bond-forming reductive elimination. These studies reveal that tetramethylammonium trifluoromethylthiolate, NMe4SCF3, exhibits a combination of fast kinetics and high chemoselectivity for transmetalation. Furthermore, Ar–SCF3 reductive elimination is fastest and highest yielding with 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (XantPhos), di-tert-butylphosphinoferrocene (DtBuPF), and tri-tert-butylphosphine (PtBu3) as ligands. These results are leveraged to develop a palladium-catalyzed method for coupling aryl iodides, -bromides, and -triflates with NMe4SCF3 using catalytic Pd(dba)2 and DtBuPF. This transformation exhibits a broad substrate scope and offers several advantages over state-of-the-art Pd-catalyzed methods for aryl–SCF3 coupling.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 11","pages":"1210–1216 1210–1216"},"PeriodicalIF":2.5,"publicationDate":"2025-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144238806","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 Reactivity of Bimetallic 2-Phosphinoimidazole Complexes of Pt at the Pt(I/I) and Pt(III/III) Oxidation States Pt（I/I）和Pt（III/III）氧化态双金属2-磷酰咪唑配合物的合成及反应活性

IF 2.5 3区化学

Organometallics Pub Date : 2025-05-19 DOI: 10.1021/acs.organomet.5c0008410.1021/acs.organomet.5c00084

Aimee L. Bangerter, James L. Corey, Taytum O. Stratton, Rebecca J. Gearhart, Scott R. Burt, Stacey J. Smith and David J. Michaelis*,

{"title":"Synthesis and Reactivity of Bimetallic 2-Phosphinoimidazole Complexes of Pt at the Pt(I/I) and Pt(III/III) Oxidation States","authors":"Aimee L. Bangerter, James L. Corey, Taytum O. Stratton, Rebecca J. Gearhart, Scott R. Burt, Stacey J. Smith and David J. Michaelis*, ","doi":"10.1021/acs.organomet.5c0008410.1021/acs.organomet.5c00084","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00084https://doi.org/10.1021/acs.organomet.5c00084","url":null,"abstract":"Bimetallic transition metal complexes provide unique opportunities in catalysis over their monometallic counterparts because of their potential to benefit from direct metal–metal interactions. These interactions, which include the formation of M–M bonds, enable access to unique oxidation states that can impact reactivity and catalysis. In this work, we synthesize and characterize (single crystal X-ray analysis) dimeric Pt complexes at the Pt(I/I) and Pt(III/III) oxidation states scaffolded on a 2-phosphinoimidazole ligand framework. DFT-generated orbitals support the formation of metal–metal bonds in these complexes. We also compare the reactivity of these two new complexes to that of our previously reported Pt(I/III) dimer in Pt-catalyzed hydroamination, cycloisomerization, and amide reduction reactions. The Lewis acidic Pt(III/III) dimer provides the highest reactivity in reactions where the platinum complex serves as a π-acid (hydroamination, cycloisomerization). In contrast, the Pt(I/I) dimer is most active in silane-mediated amide reductions that involve the addition of Pt oxidatively into the Si–H bond.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 11","pages":"1119–1123 1119–1123"},"PeriodicalIF":2.5,"publicationDate":"2025-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144238328","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 Magnesium Complexes of 2-Butene-1,4-diyl by Reduction of Dienes with a Mg–Mg-Bonded Compound 用mg - mg键合物还原二烯合成2-丁烯-1,4-二基镁配合物

IF 2.5 3区化学

Organometallics Pub Date : 2025-05-17 DOI: 10.1021/acs.organomet.5c0006710.1021/acs.organomet.5c00067

Yao Qu, Zhenzhou Sun, Hongwei Ma*, Yanxia Zhao and Xiao-Juan Yang*,

{"title":"Synthesis of Magnesium Complexes of 2-Butene-1,4-diyl by Reduction of Dienes with a Mg–Mg-Bonded Compound","authors":"Yao Qu, Zhenzhou Sun, Hongwei Ma*, Yanxia Zhao and Xiao-Juan Yang*, ","doi":"10.1021/acs.organomet.5c0006710.1021/acs.organomet.5c00067","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00067https://doi.org/10.1021/acs.organomet.5c00067","url":null,"abstract":"Reactions of the dimagnesium(I) complex [K(THF)3]2[LMg–MgL] (1, L = [(2,6-iPr2C6H3)NC(CH3)]22–) with a series of conjugated dienes, including 1,3-butadiene and its derivatives, 3-methyl-1,3-pentadiene, and 2,4-hexadiene, led to the reduction of the diene moiety to the 2-butene-1,4-diyl dianion. Bimetallic (Mg/K) complexes (2–6) of this dicarbanion were obtained, in which two Mg(II) centers are bridged by the butenediyl fragment through σ1-bonding to the carbanions, while two K+ ions are each η3-bonded by an “allyl” group of the butenediyl. Moreover, complex 7, containing a (Z,Z)-hexadienyl bridge, was also isolated upon the double dehydrogenation of hexadiene. The products were characterized by 1H and 13C NMR, UV–vis spectroscopy, and single-crystal X-ray diffraction. The work demonstrates the promising reactivity of the dimagnesium(I) complex as an electron donor and provides possible access to bis(Grignard) reagents.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 11","pages":"1148–1154 1148–1154"},"PeriodicalIF":2.5,"publicationDate":"2025-05-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144238833","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

Kinetics and Mechanism of the Protodeauration of Gold(I) β-Styrenyl Complexes 金(I) β-苯乙烯配合物原裂解动力学及机理

IF 2.5 3区化学

Organometallics Pub Date : 2025-05-16 DOI: 10.1021/acs.organomet.5c0008610.1021/acs.organomet.5c00086

Mitch Rivers, and , Ross A. Widenhoefer*,

{"title":"Kinetics and Mechanism of the Protodeauration of Gold(I) β-Styrenyl Complexes","authors":"Mitch Rivers,  and , Ross A. Widenhoefer*, ","doi":"10.1021/acs.organomet.5c0008610.1021/acs.organomet.5c00086","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00086https://doi.org/10.1021/acs.organomet.5c00086","url":null,"abstract":"Treatment of gold β-styrenyl complexes (E)-(PPh3)AuC(H)═C(H)(4-C6H4X) [X = H (1a), CN (1b), CF3 (1c), Me (1d), OMe (1e), and NMe2 (1f)] with excess acetic acid in CD2Cl2 containing PPh3 at 4 °C led to quantitative protodeauration to form the corresponding vinyl arene as the exclusive organic product. Kinetic analysis of the protodeauration of 1a-1e under these conditions established the rate law for the protodeauration of 1a: rate = k[1a][AcOH]mon, where [AcOH]mon = monomeric acetic acid and k = (4.0 ± 0.2) × 10–2 M–1 s–1 (ΔG‡ = 17.9 kcal/mol), and established the superior correlation of log(kobs) with the Hammett σ parameter (ρ = −1.26; R2 > 0.99) vis-a-vis the Hammett/Brown σ+ parameter (R2 = 0.90). These and additional observations are consistent with a mechanism for the protodeauration of complexes 1a–1e involving transfer of proton from monomeric acetic acid to the Au–C bond with concerted C–H bond formation/Au–C(σ) bond cleavage. Protodeauration of complex 1f bearing a p-NMe2 substituent was at least an order of magnitude faster than anticipated by the log(kobs)/Hammett σ relationship established for the protodeauration of complexes 1a–1e, pointing to a substitution-dependent change in the mechanism of protodeauration to a pathway initiated by the protonation of the Cα═Cβ π-bond.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 11","pages":"1165–1175 1165–1175"},"PeriodicalIF":2.5,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144238465","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

Half-Sandwich Ruthenium and Osmium Complexes with Hydrazinocurcuminoid-like Ligands. 半夹心钌锇配合物与类肼姜黄素配体。

IF 2.5 3区化学

Organometallics Pub Date : 2025-05-16 eCollection Date: 2025-06-09 DOI: 10.1021/acs.organomet.5c00082

Noemi Pagliaricci, Riccardo Pettinari, Fabio Marchetti, Sara Pagliaricci, Massimiliano Cuccioloni, Anna Maria Eleuteri, Agustín Galindo, Farzaneh Fadaei-Tirani, Kseniya Glinkina, Paul J Dyson

{"title":"Half-Sandwich Ruthenium and Osmium Complexes with Hydrazinocurcuminoid-like Ligands.","authors":"Noemi Pagliaricci, Riccardo Pettinari, Fabio Marchetti, Sara Pagliaricci, Massimiliano Cuccioloni, Anna Maria Eleuteri, Agustín Galindo, Farzaneh Fadaei-Tirani, Kseniya Glinkina, Paul J Dyson","doi":"10.1021/acs.organomet.5c00082","DOIUrl":"10.1021/acs.organomet.5c00082","url":null,"abstract":"Ruthenium and osmium half-sandwich complexes with hydrazinocurcuminoid ligands, 4,4'-((1E,1'E)-(1-(pyridin-2-yl)-1H-pyrazole-3,5-diyl)-bis-(ethene-2,1-diyl))-bis-(2-methoxyphenol) (HZPcurc) and 4,4'-((1E,1'E)-(1-(pyridin-2-yl)-1H-pyrazole-3,5-diyl)-bis-(ethene-2,1-diyl))-diphenol (HZPbdcurc), have been synthesized and characterized using NMR spectroscopy and mass spectrometry. Two of the complexes were also characterized in the solid state using X-ray diffraction analysis, confirming the pseudo-octahedral \"three-legged piano-stool\" geometry. Density functional theory (DFT) studies are performed on the ligands to evaluate their coordinating capabilities and on the resulting ruthenium and osmium complexes. The complexes are highly soluble in water and stable under physiological conditions. Their cytotoxicity against MCF-7 human breast adenocarcinoma and A2780 human ovarian carcinoma cells, both normal and cisplatin-resistant, was investigated, and good activity and selectivity with respect to nontumorigenic cells (HEK293T) were observed.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 11","pages":"1155-1164"},"PeriodicalIF":2.5,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12153055/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144281725","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

Divergent Organomagnesium Reactivity of Rigid, Dinucleating Naphthyridine Ligands: Backbone Changes with Big Impact. 刚性二核萘配体的发散性有机镁反应性：主链变化与大影响。

IF 2.5 3区化学

Organometallics Pub Date : 2025-05-16 eCollection Date: 2025-05-26 DOI: 10.1021/acs.organomet.5c00070

Errikos Kounalis, Marieke M Broekman, Puck Uyttewaal, Uladzislava Dabranskaya, Martin Lutz, Daniël L J Broere

{"title":"Divergent Organomagnesium Reactivity of Rigid, Dinucleating Naphthyridine Ligands: Backbone Changes with Big Impact.","authors":"Errikos Kounalis, Marieke M Broekman, Puck Uyttewaal, Uladzislava Dabranskaya, Martin Lutz, Daniël L J Broere","doi":"10.1021/acs.organomet.5c00070","DOIUrl":"10.1021/acs.organomet.5c00070","url":null,"abstract":"We report the synthesis and characterization of two naphthyridine-based ligands bearing pendant secondary amine and amide donors, respectively. We additionally report their deprotonation chemistry and reactivity with dialkylmagnesium and Grignard reagents. The Grignard reactions yield structurally distinct LMg2Cl2·(THF) n complexes, with the amide-based complex exhibiting reduced steric strain from the ligand around the Mg2Cl2 core. Comparison of the steric profiles of the LMg2Cl2·(THF) n complexes reveals that this reduced steric strain stems from the difference in binding modes of the ligands, which in the amide case points the bulk of sterically demanding substituents away from the Mg2Cl2 core. Reactivity of the ligands with Mg-(n-Bu)2 shows divergent outcomes: the secondary amine-based ligand forms the LMg2(n-Bu)2·(THF)2 complex cleanly, whereas the amide-based ligand produces paramagnetic species via Mg-C homolysis, triggering radical reactivity that results in ligand butylation and dimerization. These findings underscore the unique steric and electronic features of dimagnesium complexes supported by rigid, dinucleating naphthyridine ligands, highlighting how variations in ligand architecture can profoundly influence coordination chemistry and reactivity.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 10","pages":"1057-1066"},"PeriodicalIF":2.5,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12117560/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144179758","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

Half-Sandwich Ruthenium and Osmium Complexes with Hydrazinocurcuminoid-like Ligands 半夹心钌锇配合物与类肼姜黄素配体

IF 2.5 3区化学

Organometallics Pub Date : 2025-05-16 DOI: 10.1021/acs.organomet.5c0008210.1021/acs.organomet.5c00082

Noemi Pagliaricci, Riccardo Pettinari*, Fabio Marchetti, Sara Pagliaricci, Massimiliano Cuccioloni, Anna Maria Eleuteri, Agustín Galindo, Farzaneh Fadaei-Tirani, Kseniya Glinkina and Paul J. Dyson,

{"title":"Half-Sandwich Ruthenium and Osmium Complexes with Hydrazinocurcuminoid-like Ligands","authors":"Noemi Pagliaricci, Riccardo Pettinari*, Fabio Marchetti, Sara Pagliaricci, Massimiliano Cuccioloni, Anna Maria Eleuteri, Agustín Galindo, Farzaneh Fadaei-Tirani, Kseniya Glinkina and Paul J. Dyson, ","doi":"10.1021/acs.organomet.5c0008210.1021/acs.organomet.5c00082","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00082https://doi.org/10.1021/acs.organomet.5c00082","url":null,"abstract":"Ruthenium and osmium half-sandwich complexes with hydrazinocurcuminoid ligands, 4,4′-((1E,1′E)-(1-(pyridin-2-yl)-1H-pyrazole-3,5-diyl)bis(ethene-2,1-diyl))bis(2-methoxyphenol) (HZPcurc) and 4,4′-((1E,1′E)-(1-(pyridin-2-yl)-1H-pyrazole-3,5-diyl)bis(ethene-2,1-diyl))diphenol (HZPbdcurc), have been synthesized and characterized using NMR spectroscopy and mass spectrometry. Two of the complexes were also characterized in the solid state using X-ray diffraction analysis, confirming the pseudo-octahedral “three-legged piano-stool” geometry. Density functional theory (DFT) studies are performed on the ligands to evaluate their coordinating capabilities and on the resulting ruthenium and osmium complexes. The complexes are highly soluble in water and stable under physiological conditions. Their cytotoxicity against MCF-7 human breast adenocarcinoma and A2780 human ovarian carcinoma cells, both normal and cisplatin-resistant, was investigated, and good activity and selectivity with respect to nontumorigenic cells (HEK293T) were observed.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 11","pages":"1155–1164 1155–1164"},"PeriodicalIF":2.5,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.organomet.5c00082","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144238824","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

Mechanistic Study of Silylacetylene Hydroboration Catalyzed by a Cobalt PN5P Pincer Complex: Catalytic Cycles Altering the Reaction Efficiency 钴PN5P钳形配合物催化硅乙炔氢硼化的机理研究：催化循环对反应效率的影响

IF 2.5 3区化学

Organometallics Pub Date : 2025-05-15 DOI: 10.1021/acs.organomet.5c0009010.1021/acs.organomet.5c00090

J. Pablo Martínez*, Dariusz Lewandowski, Grzegorz Hreczycho* and Bartosz Trzaskowski*,

{"title":"Mechanistic Study of Silylacetylene Hydroboration Catalyzed by a Cobalt PN5P Pincer Complex: Catalytic Cycles Altering the Reaction Efficiency","authors":"J. Pablo Martínez*, Dariusz Lewandowski, Grzegorz Hreczycho* and Bartosz Trzaskowski*, ","doi":"10.1021/acs.organomet.5c0009010.1021/acs.organomet.5c00090","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00090https://doi.org/10.1021/acs.organomet.5c00090","url":null,"abstract":"The reaction mechanisms of the hydroboration of silylacetylene with pinacolborane catalyzed by a cobalt complex with a PN5P triazine pincer have been studied using density functional-theory (DFT). The calculations reveal multiple reaction routes for catalyst initiation and product formation. The cobalt complex undergoes activation via hydride transfer from pinacolborane, a process confirmed by experimental NMR analysis. Additionally, DFT results indicate that catalyst activation involves dimerization and hydrogen evolution. In contrast to the generally proposed cobalt-boryl intermediates, the active catalyst is identified as a cobalt monohydride species. During the propagation phase, cobalt monohydride preferentially reacts with silylacetylenes rather than pinacolborane, as indicated by kinetic and thermodynamic descriptors, thus impeding the formation of cobalt boryl species. This higher reactivity of alkynes in this reaction is attributed to their Brønsted acidity. The pathways leading to the hydroborated product involve hydrometallation competing with hydrogen evolution, with the latter being followed by borylation with pinacolborane, hydroalkylation, and eventually either reductive elimination or alkyne insertion. Our findings also indicate that transition state energies can be reduced by incorporating electron-withdrawing groups into the silylacetylene substrate. Enhancements in product yield are examined in relation to the silyl substituents, as well as a protocol with broader applicability, formulated under laboratory conditions.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 10","pages":"1088–1099 1088–1099"},"PeriodicalIF":2.5,"publicationDate":"2025-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.organomet.5c00090","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144133879","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

Gold(I) Complexes of ImPyDippDipp and ImPyMesMes: Biaryl L-Shaped N-Heterocyclic Carbene Analogues of IPr and IMes ImPyDippDipp和ImPyMesMes的金(I)配合物：IPr和times的双芳基l形n杂环碳类似物

IF 2.5 3区化学

Organometallics Pub Date : 2025-05-15 DOI: 10.1021/acs.organomet.5c0009310.1021/acs.organomet.5c00093

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

{"title":"Gold(I) Complexes of ImPyDippDipp and ImPyMesMes: Biaryl L-Shaped N-Heterocyclic Carbene Analogues of IPr and IMes","authors":"Yuzhuo Sha, Wenchao Chu*, Tongliang Zhou, Roger Lalancette, Roman Szostak and Michal Szostak*, ","doi":"10.1021/acs.organomet.5c0009310.1021/acs.organomet.5c00093","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00093https://doi.org/10.1021/acs.organomet.5c00093","url":null,"abstract":"Imidazol-2-ylidenes, IPr and IMes, represent by far the most important and widely utilized N-heterocyclic carbenes in organic synthesis and catalysis. Herein, we report the synthesis, catalytic activity, and structural and electronic characterization of ImPyDippDipp and ImPyMesMes, sterically bulky and easily accessible biaryl L-shaped N-heterocyclic carbene analogues of IPr and IMes. These ligands exploit the rigid imidazo[1,5-a]pyridin-3-ylidene architecture to merge the properties of the biaryl scaffold with the electron-rich characteristics of the carbene center. The catalytic activity is evaluated in the gold(I)-catalyzed hydration of alkynes and cyclization N-propargylamides, two model reactions for π-activation of alkynes that have found broad application in organic synthesis. Structural and electronic evaluation indicates that biaryl L-shaped ImPyDippDipp and ImPyMesMes ligands are more sterically demanding and more electron σ-donating and π-accepting than the classical imidazol-2-ylidnes, IPr and IMes. Both of these L-shaped ligands show excellent catalytic activity in gold(I)-catalyzed hydration of alkynes and cyclization of N-propargylamides compared to their imidazol-2-ylidene congeners, IPr and IMes. Considering the tremendous impact of imidazol-2-ylidenes in homogeneous catalysis, we anticipate that this class of biaryl L-shaped NHCs will be rapidly and widely adopted to complement IPr and IMes N-heterocyclic carbenes.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 10","pages":"1100–1107 1100–1107"},"PeriodicalIF":2.5,"publicationDate":"2025-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144134035","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