Organometallics最新文献

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Catalytic Glutathione Oxidation and Platinum(IV) Prodrug Activation via a Ruthenium-Flavin Catalyst 钌-黄素催化谷胱甘肽氧化和铂(IV)前药活化
IF 2.5 3区 化学
Organometallics Pub Date : 2025-04-16 DOI: 10.1021/acs.organomet.5c0003510.1021/acs.organomet.5c00035
Juan Sánchez-Camacho, Ana C. Carrasco, German E. Pieslinger, Álvaro Martínez, Ryszard Lobinski, Luisa Ronga and Luca Salassa*, 
{"title":"Catalytic Glutathione Oxidation and Platinum(IV) Prodrug Activation via a Ruthenium-Flavin Catalyst","authors":"Juan Sánchez-Camacho,&nbsp;Ana C. Carrasco,&nbsp;German E. Pieslinger,&nbsp;Álvaro Martínez,&nbsp;Ryszard Lobinski,&nbsp;Luisa Ronga and Luca Salassa*,&nbsp;","doi":"10.1021/acs.organomet.5c0003510.1021/acs.organomet.5c00035","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00035https://doi.org/10.1021/acs.organomet.5c00035","url":null,"abstract":"<p >Cyclopentadienyl (Cp) Ru(IV) quinoline complexes are known for their role in bioorthogonal catalysis within cellular environments, where they use endogenous GSH to deprotect profluorescent and prodrug substrates. However, their reactivity toward GSH and potential for redox-mediated therapies remain underexplored. This study presents <b>RuQ-TARF</b>, a Cp-Ru(IV) complex with a quinoline ligand linked to 2′,3′,4′,5′-tetraacetylriboflavin (<b>TARF</b>) as a redox-active moiety. Its catalytic activity in oxidizing GSH and activating a Pt(IV) prodrug of oxaliplatin was investigated. <b>RuQ-TARF</b> catalyzes the oxidation of GSH to GSSG, improving electron transfer compared to <b>RuQ</b>, its flavin-free analogue. LC–MS analysis showed that activating the Pt(IV) prodrug with GSH produces multinuclear Pt(II)-GS species. <b>RuQ-TARF</b> was additionally evaluated during coincubation with GSH and NADH under blue light, where NADH enabled faster activation of the prodrug, producing oxaliplatin as confirmed by <sup>1</sup>H and <sup>195</sup>Pt NMR. Cyclic voltammetry showed that linking <b>TARF</b> to <b>RuQ</b> improves the reversibility of redox processes, enhancing catalytic performance and supporting its use in combined GSH oxidation and prodrug activation strategies.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 8","pages":"944–951 944–951"},"PeriodicalIF":2.5,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143878298","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: Selective Benzylidene Insertion Reactions in Organoplatinum Complexes 闪光通讯:有机铂配合物中的选择性苄基插入反应
IF 2.5 3区 化学
Organometallics Pub Date : 2025-04-15 DOI: 10.1021/acs.organomet.5c0005110.1021/acs.organomet.5c00051
Mohamed E. Moustafa, Paul D. Boyle and Richard J. Puddephatt*, 
{"title":"Flash Communication: Selective Benzylidene Insertion Reactions in Organoplatinum Complexes","authors":"Mohamed E. Moustafa,&nbsp;Paul D. Boyle and Richard J. Puddephatt*,&nbsp;","doi":"10.1021/acs.organomet.5c0005110.1021/acs.organomet.5c00051","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00051https://doi.org/10.1021/acs.organomet.5c00051","url":null,"abstract":"<p >The reaction of PhCHBr<sub>2</sub> with the cycloneophylplatinum complex [Pt(CH<sub>2</sub>CMe<sub>2</sub>C<sub>6</sub>H<sub>4</sub>)(NN)], <b>1</b>, NN = 4,4’-di-<i>t</i>-butyl-2,2’-bipyridine (bubipy), gave the complex [PtBr<sub>2</sub>(CH<sub>2</sub>CMe<sub>2</sub>C<sub>6</sub>H<sub>4</sub>CHPh)(NN)], <b>2</b>, which is formed by formal oxidative insertion of benzylidene, PhCH, into the arylplatinum bond of <b>1</b>. By monitoring the reactions by <sup>1</sup>H NMR spectroscopy, intermediates were detected and shown to be products of oxidative addition [PtBr(CHBrPh)(CH<sub>2</sub>CMe<sub>2</sub>C<sub>6</sub>H<sub>4</sub>CHPh)(NN)], <b>3</b>, along with a side product [PtBr<sub>2</sub>(CH<sub>2</sub>CMe<sub>2</sub>C<sub>6</sub>H<sub>4</sub>)(NN)]. The formation of <b>2</b> gives the first example of selective benzylidene insertion reactions into an aryl–platinum bond, with potential for applications in catalysis.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 8","pages":"905–907 905–907"},"PeriodicalIF":2.5,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143878270","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
Group XI Complexes Supported by Chiral N-Heterocyclic Ligands Built on the Imidazo[1,5-a]pyridin-3-ylidene Skeleton: Synthesis, Characterization, and Evaluation in Selective Catalysis 咪唑[1,5-a]吡啶-3-吡啶骨架上手性n-杂环配体负载的XI族配合物:合成、表征和选择性催化评价
IF 2.5 3区 化学
Organometallics Pub Date : 2025-04-11 DOI: 10.1021/acs.organomet.5c0006610.1021/acs.organomet.5c00066
Chloé Stoll, Céline Besnard and Clément Mazet*, 
{"title":"Group XI Complexes Supported by Chiral N-Heterocyclic Ligands Built on the Imidazo[1,5-a]pyridin-3-ylidene Skeleton: Synthesis, Characterization, and Evaluation in Selective Catalysis","authors":"Chloé Stoll,&nbsp;Céline Besnard and Clément Mazet*,&nbsp;","doi":"10.1021/acs.organomet.5c0006610.1021/acs.organomet.5c00066","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00066https://doi.org/10.1021/acs.organomet.5c00066","url":null,"abstract":"<p >A series of copper(I), silver(I), and gold(I) complexes supported by <i>C</i><sub>1</sub>-symmetric chiral <i>N</i>-heterocyclic ligands elaborated on the imidazo[1,5-<i>a</i>]pyridin-3-ylidene core structure is reported. The flexibility of the synthesis of the imidazolium salts (X = Br, Cl) enabled to combine bulky α-<i>tert</i>butyl benzylamines at N(2) with an array of aryl substituents at C(5) that are electronically and sterically diversified. Comparative structural analysis of the copper complexes and calculation of their buried volume revealed a marked shielding of the coordination sphere of the metal center together with the possibility of varying substantially the steric environment by adequate combination of substituents at N(2) and C(5). The ability of the chiral ligands to effectively induce asymmetry in homogeneous transition metal catalysis was established by subjecting a selection of precatalysts to the Cu-catalyzed enantioselective borylative carboxamidation of vinyl arenes and the Cu-catalyzed enantioselective borylacylation of vinyl arenes.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 8","pages":"952–958 952–958"},"PeriodicalIF":2.5,"publicationDate":"2025-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143878288","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
Origin of the Electronic Effects on Regioselectivity in Ni-Catalyzed Indenone Synthesis 镍催化茚酮合成中电子效应对区域选择性的影响
IF 2.5 3区 化学
Organometallics Pub Date : 2025-04-10 DOI: 10.1021/acs.organomet.5c0000710.1021/acs.organomet.5c00007
Kaylee K. Head, Jacob L. Holley, Haley E. Roberts, Mary K. Kinsey, Sarah E. Plummer, Mary V. Raymond, Anika J. Richards, Meghan A. van Tol, Madeline G. Wall and Dale J. Wilger*, 
{"title":"Origin of the Electronic Effects on Regioselectivity in Ni-Catalyzed Indenone Synthesis","authors":"Kaylee K. Head,&nbsp;Jacob L. Holley,&nbsp;Haley E. Roberts,&nbsp;Mary K. Kinsey,&nbsp;Sarah E. Plummer,&nbsp;Mary V. Raymond,&nbsp;Anika J. Richards,&nbsp;Meghan A. van Tol,&nbsp;Madeline G. Wall and Dale J. Wilger*,&nbsp;","doi":"10.1021/acs.organomet.5c0000710.1021/acs.organomet.5c00007","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00007https://doi.org/10.1021/acs.organomet.5c00007","url":null,"abstract":"<p >The migratory insertion of an alkyne into a metal–carbon bond is a key elementary step in many reactions. For transformations that utilize unsymmetrical alkynes, reliable control over the regioselectivity of this process is required. Several factors that control alkyne migratory insertion selectivity are well-known. Other factors remain poorly understood. While substituents on an alkene or alkyne undergoing migratory insertion are known to produce electronic effects that alter the selectivity of this process, our group recently reported a Ni-catalyzed indenone synthesis in which the electronic character of the migrating aryl ligands exerted a substantial influence over regioselectivity. Herein we provide several hypothetical causes for these unusual electronic effects, and experimental evidence to support them. We determined that the previously observed electronic effects on regioselectivity are the result of unfavorable dipole–dipole interactions that develop between the migrating aryl ligands and the silyl-substituted alkynes undergoing insertion. These regioselectivity effects are anticipated to be somewhat general for alkyne migratory insertion processes at other metals, as a related Co-catalyzed indenone synthesis displays a similar electronic relationship.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 8","pages":"922–926 922–926"},"PeriodicalIF":2.5,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143878192","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
Carbon Nanotube-Supported Iron Complex Catalyzes 1-Hexene Dimerization 碳纳米管负载铁配合物催化1-己烯二聚化
IF 2.5 3区 化学
Organometallics Pub Date : 2025-04-09 DOI: 10.1021/acs.organomet.5c0010910.1021/acs.organomet.5c00109
Molly Davis, Caroline E. Arnall, Caroline M. Vanderloo, Charlotte J. Angermeier and Emmanuelle Despagnet-Ayoub*, 
{"title":"Carbon Nanotube-Supported Iron Complex Catalyzes 1-Hexene Dimerization","authors":"Molly Davis,&nbsp;Caroline E. Arnall,&nbsp;Caroline M. Vanderloo,&nbsp;Charlotte J. Angermeier and Emmanuelle Despagnet-Ayoub*,&nbsp;","doi":"10.1021/acs.organomet.5c0010910.1021/acs.organomet.5c00109","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00109https://doi.org/10.1021/acs.organomet.5c00109","url":null,"abstract":"<p >Supported catalysts for ethylene polymerization and oligomerization have gathered significant interest due to the benefits of catalyst recyclability and ease of removal from reaction media. However, reports on the oligomerization of heavy olefins remain scarce. This heterogenization process typically involves immobilizing an efficient homogeneous catalyst onto a selected support such as zeolites, silica, or metal–organic/covalent-organic frameworks. Carbon nanotubes (CNTs) present a promising support platform due to their high mechanical strength and low solubility in organic solvents. In this study, we report the heterogenization of a pyridine bis-imine iron complex on CNTs and its activity in the dimerization of 1-hexene. The CNT/iron complex was synthesized using imido linkage and characterized by TEM/EDS and inductively coupled plasma–optical emission spectroscopy to determine the distribution and loading of the catalyst. An optimal iron/CNT ratio of 1:1 by weight was identified. The system exhibited high reactivity in the dimerization of 1-hexene, achieving 94% olefin consumption and 64% C12 formation. Characterization of the resulting oligomers indicated that the CNT-supported catalyst operates via a mechanism similar to that of the homogeneous catalyst.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 8","pages":"959–963 959–963"},"PeriodicalIF":2.5,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143878395","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: Oxidative Addition of 3-Iodopyridine at a Nickel Diphosphine Complex: Probing Secondary Borane Effects 闪光通讯:3-碘吡啶在二膦镍配合物上的氧化加成:探测次生硼烷效应
IF 2.5 3区 化学
Organometallics Pub Date : 2025-04-09 DOI: 10.1021/acs.organomet.5c0007510.1021/acs.organomet.5c00075
Brady J. H. Austen,  and , Marcus W. Drover*, 
{"title":"Flash Communication: Oxidative Addition of 3-Iodopyridine at a Nickel Diphosphine Complex: Probing Secondary Borane Effects","authors":"Brady J. H. Austen,&nbsp; and ,&nbsp;Marcus W. Drover*,&nbsp;","doi":"10.1021/acs.organomet.5c0007510.1021/acs.organomet.5c00075","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00075https://doi.org/10.1021/acs.organomet.5c00075","url":null,"abstract":"<p >The catalytic cross coupling of <i>N</i>-heteroaryl electrophiles is a powerful strategy for accessing functionalized ring systems. This study explores the reactivity of [Ni(diphosphine)] complexes with 3-iodopyridine. When the diphosphine ligand features a pendent borane moiety, oxidative addition occurs, leading to the formation of a stable dimeric {Ni}<sub>2</sub> species having dative B–N interactions. These findings are contrasted against an <i>n</i>-alkyl containing ligand analogue, highlighting a secondary coordination sphere effect.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 8","pages":"908–911 908–911"},"PeriodicalIF":2.5,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143878396","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 Electronic Properties of Arene-Fused o-Carborane 芳烃-邻碳硼烷的合成及电子性能研究
IF 2.5 3区 化学
Organometallics Pub Date : 2025-04-08 DOI: 10.1021/acs.organomet.5c0002610.1021/acs.organomet.5c00026
Caixia Jia, Lili Wang*, Yan-Na Ma* and Zheng Duan*, 
{"title":"Synthesis and Electronic Properties of Arene-Fused o-Carborane","authors":"Caixia Jia,&nbsp;Lili Wang*,&nbsp;Yan-Na Ma* and Zheng Duan*,&nbsp;","doi":"10.1021/acs.organomet.5c0002610.1021/acs.organomet.5c00026","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00026https://doi.org/10.1021/acs.organomet.5c00026","url":null,"abstract":"<p >A transition-metal-free, base-mediated intramolecular C-arylation of <i>o</i>-carborane provides facile access to arene<i>-</i>fused <i>o</i>-carboranes. The new naphthyl-fused <i>o</i>-carborane <b>2,</b> as a fluoranthene analogue, was obtained with the reaction of 1-(8-Br-1-naphthyl)-<i>o</i>-carborane under basic conditions. This method is also applicable to the synthesis of biaryl-fused <i>o</i>-carboranes. The corresponding arene-fused <i>nido</i>-carborane was further obtained after deboronation with <i><sup>n</sup></i>Bu<sub>4</sub>NF. The fluorescence quantum efficiency of <b>5</b> has shown significant improvement compared to fluoranthene (Φ<sub>PL</sub>: 0.79 vs 0.2). In addition, the aromaticity of the <i>o</i>-carborane-annulated ring systems in these new compounds was studied and found to be enhanced compared to the corresponding rings of fluoranthene.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 8","pages":"938–943 938–943"},"PeriodicalIF":2.5,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143878267","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
Unsymmetrical NNE (E = S, Se) Pincer Palladium(II) Complexes: Syntheses, Structure, and Catalytic Activity in Decarboxylative Heteroarylation of Coumarin-3-carboxylic Acids 不对称NNE (E = S, Se)钳形钯(II)配合物:香豆素-3羧酸脱羧异芳基化的合成、结构和催化活性
IF 2.5 3区 化学
Organometallics Pub Date : 2025-04-04 DOI: 10.1021/acs.organomet.4c0049410.1021/acs.organomet.4c00494
Prakash N. Swami, Neha Meena, Hemant Joshi,  Aarzoo, Ram Kinkar Roy, Krishnan Rangan and Anil Kumar*, 
{"title":"Unsymmetrical NNE (E = S, Se) Pincer Palladium(II) Complexes: Syntheses, Structure, and Catalytic Activity in Decarboxylative Heteroarylation of Coumarin-3-carboxylic Acids","authors":"Prakash N. Swami,&nbsp;Neha Meena,&nbsp;Hemant Joshi,&nbsp; Aarzoo,&nbsp;Ram Kinkar Roy,&nbsp;Krishnan Rangan and Anil Kumar*,&nbsp;","doi":"10.1021/acs.organomet.4c0049410.1021/acs.organomet.4c00494","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00494https://doi.org/10.1021/acs.organomet.4c00494","url":null,"abstract":"<p >This report describes the syntheses of two novel benzoxazolyl-derived unsymmetrical NNE (E = S, Se) pincer ligands and their palladium(II) complexes. Treatment of benzoxazolyl-derived pincer ligands <b>L1</b> and <b>L2</b> with PdCl<sub>2</sub>(CH<sub>3</sub>CN)<sub>2</sub> provided complexes <b>C1</b> and <b>C2</b>, respectively, in which the NNE ligands coordinated to Pd in a tridentate pincer manner. The ligands and complexes were characterized by <sup>1</sup>H and <sup>13</sup>C Nuclear Magnetic Resonance (NMR), Fourier-transform infrared spectroscopy (FTIR), high-resolution mass spectrometry (HRMS), UV–visible, X-ray photoelectron spectroscopy (XPS), and cyclic voltammetry techniques. The structure of the ligand and its coordination mode with the palladium center was established using a single-crystal X-ray diffraction technique. The complex <b>C2</b> showed a pincer coordination mode with a distorted square planar geometry. The catalytic performance of palladium complexes <b>C1</b> and <b>C2</b> was investigated for the decarboxylative heteroarylation of coumarin-3-carboxylic acid. Notably, heteroarenes could give up to 80% of heteroarylation products in the presence of 5 mol % of the catalyst. A broad substrate of heteroarenes showed tolerance toward the developed protocol. Among complexes, the selenium ligand coordinated complex (<b>C2</b>) outperformed the sulfur ligand coordinated complex <b>C1</b>, which may be due to stronger σ-donation by the Se atom.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 8","pages":"912–921 912–921"},"PeriodicalIF":2.5,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143878237","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
Titanium Carboxylate Complexes through CO2 Capture 羧酸钛配合物通过CO2捕获
IF 2.5 3区 化学
Organometallics Pub Date : 2025-04-02 DOI: 10.1021/acs.organomet.5c0002310.1021/acs.organomet.5c00023
Marcel Eilers, Kevin Schwitalla, Marc Schmidtmann and Rüdiger Beckhaus*, 
{"title":"Titanium Carboxylate Complexes through CO2 Capture","authors":"Marcel Eilers,&nbsp;Kevin Schwitalla,&nbsp;Marc Schmidtmann and Rüdiger Beckhaus*,&nbsp;","doi":"10.1021/acs.organomet.5c0002310.1021/acs.organomet.5c00023","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00023https://doi.org/10.1021/acs.organomet.5c00023","url":null,"abstract":"<p >Addition of gaseous CO<sub>2</sub> to solutions of bis(π-η<sup>5</sup>:σ-η<sup>1</sup>-pentafulvene)titanium complexes results in the selective insertion reaction of one equivalent of O═C═O into one of the two frustrated Ti–C<sub>exo</sub> bonds under mild conditions. The formation of κ<sup>1</sup><i>O</i>- and κ<sup>2</sup><i>O</i>,<i>O</i>-carboxylate titanium complexes is observed and characterized by single crystal X-ray analysis, NMR and IR spectroscopy. The nature of Ti–O interactions is established by computational studies. The reactivity of the remaining pentafulvene ligand is demonstrated in reactions with H-acidic and multiple-bond-containing substrates. The reactions with etheric HCl results in the selective formation of Ti–Cl complexes by protonation of the second pentafulvene moiety, disregarding the carboxylate ligand. The formed chlorido complexes are used in follow-up reactions with methyllithium, resulting in the methylation of the complexes via salt metathesis reactions, and reduction of the chloride complexes with sodium amalgam results in the formation of dimeric κ<sup>1</sup><i>O</i>-μ-<i>O</i>/bridged-carboxylate Ti<sup>(III)</sup> complexes.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 7","pages":"866–874 866–874"},"PeriodicalIF":2.5,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.organomet.5c00023","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143825267","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
Nickel Complexes of 4,5-Bis(diorganophosphinomethyl)acridine Ligands 4,5-二(二有机膦甲基)吖啶配体的镍配合物
IF 2.5 3区 化学
Organometallics Pub Date : 2025-03-29 DOI: 10.1021/acs.organomet.5c0003310.1021/acs.organomet.5c00033
Maximilian Roca Jungfer, Frank Rominger, Thomas Oeser, A. Stephen K. Hashmi and Thomas Schaub*, 
{"title":"Nickel Complexes of 4,5-Bis(diorganophosphinomethyl)acridine Ligands","authors":"Maximilian Roca Jungfer,&nbsp;Frank Rominger,&nbsp;Thomas Oeser,&nbsp;A. Stephen K. Hashmi and Thomas Schaub*,&nbsp;","doi":"10.1021/acs.organomet.5c0003310.1021/acs.organomet.5c00033","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00033https://doi.org/10.1021/acs.organomet.5c00033","url":null,"abstract":"<p >In a study to expand the coordination chemistry of methylene-extended 4,5-bis(diorganophosphinomethyl)acridine ligands (L<sup>R</sup>) to first-row transition metal ions, bidentate <i>P</i>,<i>P</i>-chelated nickel complexes of these usually tridentate pincer ligands were identified. Similar to the iron complexes of these ligands, the acridines’ nitrogen atom does not coordinate to nickel, leading to the formation of nickel bisphosphine-type complexes adopting both cis- and trans-coordination modes. Nickel complexes with compositions [NiX<sub>2</sub>(κ<sup>2</sup>-L<sup>R</sup>)] (X = Cl, Br, I, CO, CN, and R = Cy, <i>i</i>Pr) were isolated and characterized. The bisphosphine ligands are weakly bound to nickel and can be transferred from [NiCl<sub>2</sub>(κ<sup>2</sup>-L<sup>R</sup>)] to [ClAu(SMe<sub>2</sub>)], giving the gold(I) cations [Au(L<sup>R</sup>)]<sup>+</sup>. The chlorido ligands are selectively exchanged for CN<sup>–</sup> during the reaction of [NiCl<sub>2</sub>(κ<sup>2</sup>-L<sup>R</sup>)] with KCN, giving <i>trans</i>-[Ni(CN)<sub>2</sub>(κ<sup>2</sup>-L<sup>Cy</sup>)]. In contrast, the nickel(0) carbonyls [Ni(CO)<sub>2</sub>(κ<sup>2</sup>-L<sup>R</sup>)] form in photochemical reactions from [Ni(CO)<sub>2</sub>(PPh<sub>3</sub>)<sub>2</sub>] and L<sup>R</sup> in partially reversible reactions and are intrinsically unstable in solution.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 7","pages":"882–891 882–891"},"PeriodicalIF":2.5,"publicationDate":"2025-03-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143825296","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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