Organometallics最新文献

{"title":"[B(O2C2(CF3)4)2]− ([FPB]−): Repurposing This Weakly Coordinating Anion for Solid-State Molecular Organometallic (SMOM) Chemistry","authors":"Kristof M. Altus,&nbsp;M. Arif Sajjad,&nbsp;Stuart A. Macgregor* and Andrew S. Weller*,&nbsp;","doi":"10.1021/acs.organomet.5c0011210.1021/acs.organomet.5c00112","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00112https://doi.org/10.1021/acs.organomet.5c00112","url":null,"abstract":"<p >The perfluoropinacol borate-based anion [B(O₂C₂(CF₃)₄)₂]⁻, <b>[FPB]</b>^–, is developed as a weakly coordinating anion for single-crystal to single-crystal organometallic solid/gas reactivity, resulting in the isolation and characterization (including periodic DFT and IGMH analysis) of the σ-alkane complex [Rh(Cy₂PCH₂CH₂PCy₂)(<i>exo</i>-η²η²-norbornane)][FPB]. The synthetically useful solvent-free Na⁺ salt, Na[FPB], and oxonium acid [H(OEt₂)₂][FPB] are also reported.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 10","pages":"1018–1021 1018–1021"},"PeriodicalIF":2.5,"publicationDate":"2025-05-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.organomet.5c00112","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144133851","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":"[B(O₂C₂(CF₃)₄)₂]^- ([FPB]^-): Repurposing This Weakly Coordinating Anion for Solid-State Molecular Organometallic (SMOM) Chemistry.","authors":"Kristof M Altus, M Arif Sajjad, Stuart A Macgregor, Andrew S Weller","doi":"10.1021/acs.organomet.5c00112","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00112","url":null,"abstract":"<p><p>The perfluoropinacol borate-based anion [B-(O₂C₂(CF₃)₄)₂]^-, <b>[FPB]</b> ^-, is developed as a weakly coordinating anion for single-crystal to single-crystal organometallic solid/gas reactivity, resulting in the isolation and characterization (including periodic DFT and IGMH analysis) of the σ-alkane complex [Rh-(Cy₂PCH₂CH₂PCy₂)-(<i>exo</i>-η²η²-norbornane)]-[FPB]. The synthetically useful solvent-free Na⁺ salt, Na-[FPB], and oxonium acid [H-(OEt₂)₂]-[FPB] are also reported.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 10","pages":"1018-1021"},"PeriodicalIF":2.5,"publicationDate":"2025-05-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12117562/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144179542","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":"(Trialkylsilyl)germanes (tBuMeRSi)GeH3 (R = Me, tBu)","authors":"Philipp Schmid,&nbsp;Karin Bartl,&nbsp;Robert Saf,&nbsp;Takahiro Sasamori,&nbsp;Vladimir Ya. Lee* and Frank Uhlig*,&nbsp;","doi":"10.1021/acs.organomet.5c0008810.1021/acs.organomet.5c00088","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00088https://doi.org/10.1021/acs.organomet.5c00088","url":null,"abstract":"<p >Stable (trialkylsilyl)germanes (^<i>t</i>BuMeRSi)GeH₃ (R = Me, ^<i>t</i>Bu) were prepared, using a novel synthetic approach, and characterized. This approach includes the initial preparation of the (trialkylsilyl)(<i>p</i>-tolyl)germanes (^<i>t</i>BuMeRSi)Ge(<i>p</i>-tolyl)H₂, chlorodearylation of which produced (trialkylsilyl)chlorogermanes (^<i>t</i>BuMeRSi)GeClH₂, which were finally reacted with LiAlH₄ to produce the desired (trialkylsilyl)germanes (^<i>t</i>BuMeRSi)GeH₃. These compounds have the potential to be precursors for the production of germanium nanoparticles and oligomers, as the prospective materials of the new generation.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 9","pages":"1000–1005 1000–1005"},"PeriodicalIF":2.5,"publicationDate":"2025-04-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143934223","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":"Synthesis and Application of PN-Supported Mn(I) Carbonyl Alkyl Complexes.","authors":"Claudia Rabijasz, Stefan Weber, Berthold Stöger, Karl Kirchner","doi":"10.1021/acs.organomet.5c00095","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00095","url":null,"abstract":"<p><p>This work comprises the synthesis and characterization of aminophosphine (PN)-derived Mn(I) carbonyl complexes and the preliminary investigation of their alkylated congeners for catalytic applications. The complexes <i>fac</i>-[Mn(PN)(CO)₃Br] are obtained from the reaction of Mn(CO)₅Br with the bidentate ligand PN = R₂N(CH₂)₂PR'₂, where R = Me, Et, and pyrrolidine and R' = Ph, <i>i</i>Pr, and Cy. Treatment of <i>fac</i>-[Mn(PN)(CO)₃Br] with AgOTf yields <i>fac</i>-[Mn(PN)(CO)₃OTf]. Upon reaction of <i>fac</i>-[Mn(PN)(CO)₃OTf] with MeLi (R' = alkyl) or MeMgCl (R' = aryl), <i>fac</i>-[Mn(PN)(CO)₃Me] is formed. <i>fac</i>-[Mn(P^CyN^Me)(CO)₃Me] and <i>fac</i>-[Mn(P^PhN^Me)(CO)₃Me] are identified as the best catalysts for the dimerization of phenylacetylene and the hydroboration of 4-chlorostyrene, respectively.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 9","pages":"1006-1011"},"PeriodicalIF":2.5,"publicationDate":"2025-04-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12076549/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144074858","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: S–N Bond Cleavage in Benzisothiazol Affords Complexes Related to [FeFe]-Hydrogenases Active Site with Peptidic-Type Bridge","authors":"Mohammad J. Uddin,&nbsp;Subas Rajbangshi,&nbsp;Shariff E. Kabir*,&nbsp;Vladimir N. Nesterov,&nbsp;Catherine Elleouet*,&nbsp;Shishir Ghosh* and Philippe Schollhammer*,&nbsp;","doi":"10.1021/acs.organomet.5c0009810.1021/acs.organomet.5c00098","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00098https://doi.org/10.1021/acs.organomet.5c00098","url":null,"abstract":"<p >The reaction of [Fe₃(CO)₁₂] with 1,2-benzisothiazol-3(2<i>H</i>)-one affords a route to the di-iron complex [Fe₂(CO)₆(μ-S{C₆H₄}CONH)] (<b>1</b>) featuring a {Fe₂SN} butterfly core with a peptide-like unit in close proximity to the di-iron site. Redox behaviors of <b>1</b> and its substituted derivatives [Fe₂(CO)_6-x(PPh₃)_<i>x</i>(μ-S{C₆H₄}CONH)] (x = 1, 2) have been preliminarily investigated.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 9","pages":"965–969 965–969"},"PeriodicalIF":2.5,"publicationDate":"2025-04-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143934547","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":"Synthesis and Application of PN-Supported Mn(I) Carbonyl Alkyl Complexes","authors":"Claudia Rabijasz,&nbsp;Stefan Weber*,&nbsp;Berthold Stöger and Karl Kirchner*,&nbsp;","doi":"10.1021/acs.organomet.5c0009510.1021/acs.organomet.5c00095","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00095https://doi.org/10.1021/acs.organomet.5c00095","url":null,"abstract":"<p >This work comprises the synthesis and characterization of aminophosphine (PN)-derived Mn(I) carbonyl complexes and the preliminary investigation of their alkylated congeners for catalytic applications. The complexes <i>fac</i>-[Mn(PN)(CO)₃Br] are obtained from the reaction of Mn(CO)₅Br with the bidentate ligand PN = R₂N(CH₂)₂PR′₂, where R = Me, Et, and pyrrolidine and R′ = Ph, <i>i</i>Pr, and Cy. Treatment of <i>fac</i>-[Mn(PN)(CO)₃Br] with AgOTf yields <i>fac</i>-[Mn(PN)(CO)₃OTf]. Upon reaction of <i>fac</i>-[Mn(PN)(CO)₃OTf] with MeLi (R′ = alkyl) or MeMgCl (R′ = aryl), <i>fac</i>-[Mn(PN)(CO)₃Me] is formed. <i>fac</i>-[Mn(P^CyN^Me)(CO)₃Me] and <i>fac</i>-[Mn(P^PhN^Me)(CO)₃Me] are identified as the best catalysts for the dimerization of phenylacetylene and the hydroboration of 4-chlorostyrene, respectively.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 9","pages":"1006–1011 1006–1011"},"PeriodicalIF":2.5,"publicationDate":"2025-04-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.organomet.5c00095","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143934462","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: Unexpected Oxidative Alkene Cleavage Behavior of a Molecular Molybdenum Bis(dithiolene) Catalyst","authors":"Beria Tanriover,&nbsp;S. M. Supundrika Subasinghe and Neal P. Mankad*,&nbsp;","doi":"10.1021/acs.organomet.5c0009910.1021/acs.organomet.5c00099","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00099https://doi.org/10.1021/acs.organomet.5c00099","url":null,"abstract":"<p >Whereas homogeneous molybdenum catalysis typically promotes alkene epoxidation with peroxide oxidants, here, a molybdenum bis(dithiolene) compound is shown to instead catalyze oxidative alkene cleavage, resulting in carbonyl products akin to ozonolysis reactions. A mechanism involving O₂ transfer from a Mo(O)(η²-O₂) intermediate to the alkenes to form 1,2-dioxetanes is proposed with support from DFT calculations.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 9","pages":"970–972 970–972"},"PeriodicalIF":2.5,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143933905","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":"(Imido)tungsten-Alkylidene-Catalyzed [2+2+1]-Cycloaddition Reaction of 3,3-Disubstituted Cyclopropenes and Internal Alkynes Giving Multisubstituted Cyclopentadienes","authors":"Takuya Akiyama,&nbsp;Akira Yamamoto,&nbsp;Tao Kasahara,&nbsp;Tetsuro Kusamoto and Hayato Tsurugi*,&nbsp;","doi":"10.1021/acs.organomet.5c0006210.1021/acs.organomet.5c00062","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00062https://doi.org/10.1021/acs.organomet.5c00062","url":null,"abstract":"<p >Schrock-type alkylidene complexes, especially imido ligand-supported metal alkylidene complexes, have been used as catalysts and reagents for C–C multiple bond-forming reactions involving unsaturated organic compounds. Herein, we report that an imidotungsten(IV) complex, WCl₂(=NDipp)(P(OMe)₃)₃, catalyzes a [2+2+1]-cycloaddition reaction of 3,3-disubstituted cyclopropenes and 2 equiv of alkynes, giving multisubstituted cyclopentadienes. The initial step of this catalytic reaction is ring-opening of a cyclopropene by the (imido)tungsten(IV) complex to form an (imido)tungsten vinylalkylidene species. Stoichiometric reactions of the (imido)tungsten vinylalkylidene complex and an η²-alkyne tungsten complex as well as density functional theory (DFT) calculations revealed the reaction mechanism, in which two consecutive metatheses of the (imido)tungsten vinylalkylidene species and two alkynes followed by reductive elimination afford the multisubstituted cyclopentadiene along with a regeneration of an (imido)tungsten(IV) species.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 10","pages":"1047–1056 1047–1056"},"PeriodicalIF":2.5,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144133822","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":"Investigations of the Reaction of HB(pin) with Tris(amido) Y(III) Complexes","authors":"Rana B. Abdu,&nbsp; and ,&nbsp;Courtney C. Roberts*,&nbsp;","doi":"10.1021/acs.organomet.5c0006810.1021/acs.organomet.5c00068","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00068https://doi.org/10.1021/acs.organomet.5c00068","url":null,"abstract":"<p >Transmetallation, or transfer of a group between metals or metalloids, is arguably the most understudied elementary organometallic step, especially with early transition metal complexes. In this work, the reactivity of the organoborane, HB(pin), with yttrium complexes bearing a tris(amido) redox-active ligand was investigated. B–O bond cleavage was observed instead of the expected B–H bond cleavage that would result from transmetallation. Additionally, the tris(amido) ligand was transferred from yttrium to boron. New boron complexes (<b>2</b>) and (<b>3</b>) were synthesized and characterized and an intermediate Y–B complex (<b>4</b>) featuring the B–O bond cleavage is also reported. This work demonstrates the incompatibility of HB(pin) as a transmetallating reagent for yttrium complexes bearing a tris(amido) ligand.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 9","pages":"995–999 995–999"},"PeriodicalIF":2.5,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143933743","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":"Formation of Bisvinylidene Complexes through Consecutive Alkyne–Vinylidene Rearrangements","authors":"Marcus Korb*,&nbsp; and ,&nbsp;Paul J. Low,&nbsp;","doi":"10.1021/acs.organomet.5c0002210.1021/acs.organomet.5c00022","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00022https://doi.org/10.1021/acs.organomet.5c00022","url":null,"abstract":"<p >The <i>ortho</i>-, <i>meta</i>-, or <i>para-</i>bis-phenylethynyl benzenes (BPEBs), <i>o</i>-/<i>m</i>-/<i>p</i>-(PhC≡C)₂–C₆H₄, were converted into bis(vinylidene) complexes by two consecutive 1,2-migration reactions within the coordination sphere of half-sandwich complexes [M^II(dppe)Cp]⁺ (M^II = Ru^II, Fe^II). The yield of the novel bis(vinylidene) complexes <i>o</i>-/<i>m</i>-/<i>p</i>-[{Cp(dppe)Ru═C═C(Ph)}₂–C₆H₄]²⁺ is affected by the spatial proximity of the substituents and decreases from 90% (<i>para</i>) to 0% (<i>ortho</i>). The yield of the intermediate monovinylidene species [Ru(═C═C{<i>o</i>-/<i>m</i>-/<i>p</i>-(Ph–C≡C)–C₆H₄}Ph)(dppe)Cp]⁺ isolated under these conditions increases accordingly. Comparison of transition states of the rearrangement process (^<b>R</b><b>TS</b>) obtained from computational methods (DFT) confirmed an increased activation barrier (<i>E</i>_A) for <i>o</i>-BPEB (<i>E</i>_A = 107 kJ/mol) compared to the <i>p</i>-BPEB analogue (<i>E</i>_A = 80 kJ/mol). This steric impost on the double rearrangement was further quantified by buried volume calculations (<i>V</i>_B^total) of the vinylidene moieties when located around the central phenylene ring in <i>ortho</i>-, <i>meta</i>-, or <i>para-</i>positions, which decreases from 43–46% (<i>o</i>-), to 22–31% (<i>m</i>-), and 16% (<i>p</i>-). Moving from <i>p-</i>BPEB to 1,9-bis(phenylethynyl)anthracene or 1,1′-bis(phenylethynyl)ferrocene motifs reduced the yields of the bisvinylidenes from 90% to 66% and 40%, respectively. Electrochemical measurement confirmed that the nature of the positive charges in monovinylidene complexes {Ru(═C═CArAr′)(dppe)Cp}⁺ and {Ru(dppe)Cp}⁺ fragments is not repulsive, indicating that substrates with more than two alkynyl functionalities can be converted.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 9","pages":"982–994 982–994"},"PeriodicalIF":2.5,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143933920","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}