Organometallics最新文献

{"title":"Amidinate- and Dithiolene-Based Silicon Complexes.","authors":"Yuzhong Wang, John C Johnson, Kayla G Palmer, Pingrong Wei, Earle R Adams, Mitchell E Lahm, Henry F Schaefer, Gregory H Robinson","doi":"10.1021/acs.organomet.5c00038","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00038","url":null,"abstract":"<p><p>Reactions of the amidinato-silylene chloride PhC( ^<i>t</i> BuN)₂SiCl (<b>1</b>) with imidazole-based dithione dimer <b>2</b>, lithium dithiolene radical <b>3</b>, and dithiolate dimer <b>4</b> result in the synthesis of a series of silicon complexes <b>5</b>-<b>7</b>, respectively, containing both amidinato and dithiolene ligands. <b>7</b> is the first structurally characterized silicon(II) dithiolene complex. The structural and bonding characteristics of <b>5</b>-<b>7</b> have been probed by both experimental and theoretical methods.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 7","pages":"802-806"},"PeriodicalIF":2.5,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12001252/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143951166","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}

{"title":"Isolation of Silylene-Ligated Plumbyliumylidene and Diplumbyne","authors":"Kainan Yu,&nbsp;Fanshu Cao,&nbsp;Xi Chen and Zhenbo Mo*,&nbsp;","doi":"10.1021/acs.organomet.5c0002810.1021/acs.organomet.5c00028","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00028https://doi.org/10.1021/acs.organomet.5c00028","url":null,"abstract":"<p >In this study, we present the synthesis and characterization of bis(silylene)-ligated plumbyliumylidene and silylene-ligated diplumbyne. Plumbyliumylidene <b>2</b> was obtained through ion–exchange reaction of the bis(silylene)amido lead(II) bromide complex <b>1</b> with one equivalent of Na[BAr^F₄] (Ar^F = 3,5-(CF₃)₂-C₆H₃). Density functional theory calculations confirmed the presence of a lone pair on the lead atom in <b>2</b>. The reduction of compound <b>2</b> yielded silylene-ligated diplumbyne <b>3</b>, which possesses a Pb–Pb single bond and one lone pair on each lead atom. Remarkably, compound <b>3</b> underwent single-electron oxidation to regenerate plumbyliumylidene <b>2</b>, demonstrating a rare redox cycle between the Pb(I) and Pb(II) states. This study enhances the understanding of the electronic structures and redox behavior of low-valent lead compounds.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 7","pages":"792–797 792–797"},"PeriodicalIF":2.5,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143825361","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}

{"title":"Flash Communication: Mononuclear Metallacycle Mechanism in Binuclear Cr/PNCNP Catalyst May Trigger the Switch from Ethylene Trimerization into Tetramerization","authors":"Jiale Peng,&nbsp; and ,&nbsp;Zhen Liu*,&nbsp;","doi":"10.1021/acs.organomet.5c0003610.1021/acs.organomet.5c00036","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00036https://doi.org/10.1021/acs.organomet.5c00036","url":null,"abstract":"<p >An interesting switch from ethylene trimerization to tetramerization induced by the length of carbon linkers with the Cr/PNCNP catalyst has been investigated by density functional theory (DFT) methods. Structural analysis suggested that incorporating an additional methylene group into the ligand backbone may facilitate the generation of binuclear Cr species with a binding mode of (η²-<i>P</i>,<i>N</i>). Instead of the previously proposed bimetallic route, further DFT calculations indicated that a monomeric ring expansion mechanism might be responsible for the selective formation of 1-octene, which is consistent with the previous deuterium labeling experiment and crystallographic characterization.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 7","pages":"798–801 798–801"},"PeriodicalIF":2.5,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143825363","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}

{"title":"Amidinate- and Dithiolene-Based Silicon Complexes","authors":"Yuzhong Wang,&nbsp;John C. Johnson,&nbsp;Kayla G. Palmer,&nbsp;Pingrong Wei,&nbsp;Earle R. Adams,&nbsp;Mitchell E. Lahm,&nbsp;Henry F. Schaefer III and Gregory H. Robinson*,&nbsp;","doi":"10.1021/acs.organomet.5c0003810.1021/acs.organomet.5c00038","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00038https://doi.org/10.1021/acs.organomet.5c00038","url":null,"abstract":"<p >Reactions of the amidinato-silylene chloride PhC(^<i>t</i>BuN)₂SiCl (<b>1</b>) with imidazole-based dithione dimer <b>2</b>, lithium dithiolene radical <b>3</b>, and dithiolate dimer <b>4</b> result in the synthesis of a series of silicon complexes <b>5</b>–<b>7</b>, respectively, containing both amidinato and dithiolene ligands. <b>7</b> is the first structurally characterized silicon(II) dithiolene complex. The structural and bonding characteristics of <b>5</b>–<b>7</b> have been probed by both experimental and theoretical methods.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 7","pages":"802–806 802–806"},"PeriodicalIF":2.5,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.organomet.5c00038","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143825360","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}

{"title":"Flash Communication: Cyanophosphide Transfer Reactions","authors":"Ayu Afiqah Nasrullah,&nbsp;Malte Fischer,&nbsp;Fabian Dankert,&nbsp;Eszter Barath* and Christian Hering-Junghans*,&nbsp;","doi":"10.1021/acs.organomet.5c0001210.1021/acs.organomet.5c00012","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00012https://doi.org/10.1021/acs.organomet.5c00012","url":null,"abstract":"<p >Cyanophosphides of the general form [RPCN]⁻ can be viewed as cyanide adducts of phosphinidenes and are phosphorus species in the (+1)-oxidation state. We have recently reported on the stable cyanophosphide [^DippTerPCN]K (^DippTer = 2,6-Dipp₂C₆H₃, Dipp = 2,6-<i>i</i>PrC₆H₃) and now investigate its reactions with ECl_<i>n</i> (E = Ge, <i>n</i> = 2; E = P, As, <i>n</i> = 3) in either salt metathesis or base-assisted dehydrohalogenation reactions. In the case of GeCl₂, salt metathesis with [^DippTerPCN]K afforded the dimer of a chlorogermylene [^DippTerP(CN)GeCl]₂. When only 0.5 equiv of GeCl₂ was used, the diphosphanylgermylene [^DippTerP(CN)]₂Ge was generated in solution. With ECl₃ (E = P, As), facile cyanophosphide transfer was achieved from ^DippTerP(H)CN in NEt₃-assisted dehydrohalogenation, giving diphosphanes or arsaphosphanes of the type ^DippTerP(CN)ECl₂ (E = P, As), respectively.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 7","pages":"788–791 788–791"},"PeriodicalIF":2.5,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.organomet.5c00012","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143825274","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}

{"title":"Silver Instead of Gold in Nitronyl Nitroxide Chemistry","authors":"Igor A. Zayakin,&nbsp;Galina V. Romanenko,&nbsp;Alexander A. Korlyukov and Evgeny V. Tretyakov*,&nbsp;","doi":"10.1021/acs.organomet.5c0004210.1021/acs.organomet.5c00042","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00042https://doi.org/10.1021/acs.organomet.5c00042","url":null,"abstract":"<p >A nitronyl nitroxide organosilver derivative─an accessible and effective partner for cross-coupling of aryl- and heteroaryl halides─is reported for the first time. The novel cross-coupling method is based on preparation of an organosilver reagent containing a bulky N-heterocyclic carbene ligand, namely, SIPrAgNN, and a catalytic system consisting of Pd₂dba₃·CHCl₃ and phosphine ligand ^MeCgPPh having an adamantane-like framework. The newly developed protocol was found to be well-compatible with various aryl- and heteroaryl halides, thus expanding the scope of directed synthesis of functionalized nitronyl nitroxide radicals and high-spin molecules.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 7","pages":"892–898 892–898"},"PeriodicalIF":2.5,"publicationDate":"2025-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143825237","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}

{"title":"Expanding Perchlorate Use for C–H Oxidative Transformations: A Tandem Photo- and Iron-Catalytic Strategy","authors":"Writhabrata Sarkar,&nbsp; and ,&nbsp;Nathaniel K. Szymczak*,&nbsp;","doi":"10.1021/acs.organomet.4c0051610.1021/acs.organomet.4c00516","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00516https://doi.org/10.1021/acs.organomet.4c00516","url":null,"abstract":"<p >We report an iron-catalyzed, light-driven method to enable the use of perchlorate (ClO₄^–) to promote C–H oxygenation reactions. In comparison to thermal reactions, introduction of an anthraquinone (AQ) photocatalyst provided distinct reaction outcomes that are proposed to be facilitated by distinct hydrogen atom transfer reactivity. Acyclic substrates such as di- and triphenylmethane were oxygenated to form ketones or alcohols, while benzylic substrates containing S or N heteroatoms underwent C(sp³)–X (X = S or N) oxidative cleavage to form aldehydes. Appended aniline hydrogen bonds (H-bonds) within the ligand’s secondary sphere serve a primary role to facilitate both reactions.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 7","pages":"777–782 777–782"},"PeriodicalIF":2.5,"publicationDate":"2025-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143825234","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}

{"title":"Computational Insights into the Effect of Ligand Redox Properties on Reductive Elimination from Au(III), Pd(II), and Pt(II) Complexes","authors":"Saba Hadidi,&nbsp;Robert Stranger,&nbsp;Zhenyang Lin* and Alireza Ariafard*,&nbsp;","doi":"10.1021/acs.organomet.4c0048510.1021/acs.organomet.4c00485","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00485https://doi.org/10.1021/acs.organomet.4c00485","url":null,"abstract":"<p >We computationally investigated the Ar–Ar reductive elimination process in a series of biaryl Au(III), Pd(II), and Pt(II) complexes to explore the factors that govern the activation free energy associated with C–C coupling (Δ<i>G</i>^‡). Contrary to conventional beliefs that emphasize metal–Ar bond strength as the primary determinant for the ease of reductive elimination, our density functional theory (DFT) calculations reveal that the key factor is the oxidation susceptibility of the Ar ligands in their anionic forms: the easier the oxidation of Ar^–, the lower the activation free energy (Δ<i>G</i>^‡). Indeed, we found that Δ<i>G</i>^‡ strongly correlates with the reduction potential for the reaction Ar^• + e^– → Ar^– (<i>E</i>°(Ar)). We further demonstrate that variations in complex net charge and metal center significantly influence the electron-accepting ability of the metal center in the transition state, thereby affecting the ease of reductive elimination. Notably, the effects of these factors (net charge and metal center) on the activation barrier were found to be largely independent of the nature of the Ar ligands.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 6","pages":"729–736 729–736"},"PeriodicalIF":2.5,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143675915","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}

{"title":"Activation of B–C Bonds in [BArF24]− (BArF24 = Tetrakis(3,5-bis(trifluoromethyl)phenyl)borate) By Gold(I) Compounds With 1,1′-bis(phosphino)metallocene Ligands","authors":"Tyler J. Roberts,&nbsp;Ava G. Katz,&nbsp;Anna E. Boggess,&nbsp;Jennifer K. Soika,&nbsp;Eric W. Reinheimer and Chip Nataro*,&nbsp;","doi":"10.1021/acs.organomet.5c0001410.1021/acs.organomet.5c00014","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00014https://doi.org/10.1021/acs.organomet.5c00014","url":null,"abstract":"<p >Tetrakis(3,5-bis(trifluoromethyl)phenyl)borate ([BArF₂₄]⁻) stabilizes reactive cations; however, compounds capable of activating a B–C bond in this anion exist. We investigated the catalytic activity of gold(I) compounds with bis(phosphino)metallocene ligands, [(AuCl)₂(μ-PP)] (PP = 1,1′-bis(diphenylphosphino)ferrocene (dppf), 1,1′-bis(di<i>iso</i>-propylphosphino)ferrocene (dippf), 1,1′-bis(dicyclohexylphosphino)ferrocene (dcpf), 1,1′-bis(di<i>tert</i>-butylphosphino)ferrocene (dtbpf), 1-diphenylphosphino-1′- di<i>tert</i>-butylphosphino-ferrocene (dppdtbpf), or 1,1′-bis(diphenylphosphino)ruthenocene (dppr)). These compounds displayed minimal catalytic activity unless Na[BArF₂₄] was added, though the active species remains unidentified. Reactions of Na[BArF₂₄] with [(AuCl)₂(μ-PP)] revealed [(AuCl)₂(μ-PP)] (PP = dppf, dippf, dcpf, dtbpf, or dppdtbpf), gave single products, [(AuAr^F)₂(μ-PP)] (Ar^F = 3,5-C₆H₃(CF₃)₂), by ³¹P{¹H} NMR spectroscopy. These were characterized, and X-ray structures of three compounds (PP = dppf, dippf, or dtbpf) were determined. For dtbpf, an intermediate compound, [Au₂(μ-Ar^F)(μ-dtbpf)][BArF₂₄], was isolated and structurally characterized. The [(AuAr^F)₂(μ-PP)] and related [(AuPh)₂(μ-PP)] compounds were also prepared by the addition of RB(OH)₂ (R = Ar^F or Ph) to [(AuCl)₂(μ-PP)]. X-ray structures of [(AuPh)₂(μ-PP)] (PP = dppf or dcpf) were determined. Their electrochemistry was investigated by cyclic voltammetry. The role of the ferrocenyl backbone of the ligands was examined by performing reactions in the presence of chemical oxidants. These reactions provide suggest a combination of the ferrocenyl backbone, the substituents on the phosphorus atoms, and the [B(aryl)₄]⁻ play significant roles in this chemistry.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 8","pages":"927–937 927–937"},"PeriodicalIF":2.5,"publicationDate":"2025-03-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143878364","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}

{"title":"Flash Communication: Pd2Zn2 Clusters from the Reduction of Palladium(II) Dichloride Precursors with Metallic Zinc","authors":"Georgina Rai,&nbsp;Martí Garçon,&nbsp;Philip W. Miller and Mark R. Crimmin*,&nbsp;","doi":"10.1021/acs.organomet.4c0050610.1021/acs.organomet.4c00506","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00506https://doi.org/10.1021/acs.organomet.4c00506","url":null,"abstract":"<p >We report the synthesis and solid-state characterization of two unusual Pd₂Zn₂ clusters formed from the partial reduction of [PdL₂Cl₂] precursors (L₂ = dcpe or dppe) with metallic zinc. The new clusters have been characterized by single crystal X-ray diffraction and contain a Pd₂Zn₂Cl₃ core capped by two chelating phosphine ligands with Zn in the formal +1.5 oxidation state. While they possess a near tetrahedral arrangement of metal ions, calculations and bonding analysis (NBO, AIM) suggest that there is limited Zn- - -Zn bonding in these species. Characterization in the solution state is suggestive of dynamic behavior on dissolution, with both diamagnetic and paramagnetic species observed by NMR and EPR spectroscopy. One of these Pd₂Zn₂ clusters was shown to be an effective precursor for the homocoupling of an aryl bromide.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 6","pages":"716–719 716–719"},"PeriodicalIF":2.5,"publicationDate":"2025-03-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.organomet.4c00506","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143675898","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}