Organometallics最新文献

{"title":"1,4-Diphosphorinane Synthesis at a Cationic Aluminum(III) Center","authors":"Gabriel J. Jobin,&nbsp;Brady J. H. Austen and Marcus W. Drover*,&nbsp;","doi":"10.1021/acs.organomet.4c0041510.1021/acs.organomet.4c00415","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00415https://doi.org/10.1021/acs.organomet.4c00415","url":null,"abstract":"<p >Lewis acidic group 13 cations are useful mediators of small-molecule and catalytic reactivity alike. Previous work has elaborated on the use of bulky β-diketiminate Al(III) cations for the cycloaddition and intermolecular coupling of alkene substrates, giving new [Al]–C bonds. Motivated by a desire to prepare aluminum/phosphorus-containing ambiphilic ligands, here we probe the intramolecular reactivity of mono- and diphosphines bearing a pendent alkene group. Despite the drive for Al–P bond formation (as shown by control experiments), reaction of a specialized allyl-appended diphosphine results in rapid cyclization, producing an aluminum-bound 1,4-diphosphorinane (six-membered ring). Together, this contribution offers a complementary route toward this class of molecule and emphasizes the importance of substrate design characteristics such as phosphorus/alkene(β-carbon) linker length to accessing productive cyclization. The subsequent reactivity of this heterocycle, including coordination chemistry with gold(I), are additionally shared.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 1","pages":"148–157 148–157"},"PeriodicalIF":2.5,"publicationDate":"2024-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143085390","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":"Dissecting Transmetalation Reactions at the Molecular Level: Aryl Transfer in Copper-Tetraarylborate Complexes","authors":"Finn Kraft,&nbsp;Marcel Sommer,&nbsp;Aleksandr Y. Pereverzev,&nbsp;Jana Roithová*,&nbsp;Thomas Auth* and Konrad Koszinowski*,&nbsp;","doi":"10.1021/acs.organomet.4c0030410.1021/acs.organomet.4c00304","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00304https://doi.org/10.1021/acs.organomet.4c00304","url":null,"abstract":"<p >Boron–copper transmetalation reactions are practically important, but their detailed mechanisms remain elusive. To improve our understanding of these transformations, we have analyzed the systems Cu⁺/(BAr^X₄)⁻ (Ar^X = <i>p</i>-X–C₆H₄ with X = OMe, Me, H, F, Cl, CF₃) by a combination of NMR spectroscopy, ESI-mass spectrometry, gas-phase experiments, and quantum chemical calculations. By probing the gas-phase fragmentation of mass-selected adducts of the type [Cu(BAr^X₄)(BPh₄)]⁻ and [(MeCN)₂Cu₂(BAr^X₄)]⁺, we obtain intimate insight into the microscopic reactivity of these model complexes. In all cases, transmetalation reactions occur, the relative efficiency of which depends on the electronic properties of the aryl groups, the charge of the complex, and the number of solvent molecules bound to the latter. Specifically, electron-rich aryl groups show a higher tendency toward being transferred to copper than their electron-poor counterparts, whereas the addition of individual MeCN molecules diminishes the propensity toward transmetalation. The quantum chemical calculations are essential for the interpretation of the experimental results by providing structural and thermochemical information. The trends derived from the present gas-phase models promise to help in the mechanistic analysis of boron–copper transmetalation in solution.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 4","pages":"547–559 547–559"},"PeriodicalIF":2.5,"publicationDate":"2024-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.organomet.4c00304","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143473682","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":"Synthesis and Structure of Silyl-Substituted Bis(cyclopentadienyl) Scandium(III) Halide Complexes","authors":"Joseph Q. Nguyen,&nbsp;Lauren M. Anderson-Sanchez,&nbsp;Joseph W. Ziller and William J. Evans*,&nbsp;","doi":"10.1021/acs.organomet.4c0041210.1021/acs.organomet.4c00412","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00412https://doi.org/10.1021/acs.organomet.4c00412","url":null,"abstract":"<p >Despite the importance of bis(cyclopentadienyl) scandium(III) halide complexes as precursors in the development of scandium metallocene chemistry, relatively few examples of this class have been structurally characterized. Since the cyclopentadienyl ring substitution pattern and the halide identity can have a major influence on organoscandium complex synthesis and reactivity, it is critical to have a variety of well-characterized [(C₅R₅)₂ScX]_n starting materials (R = H, alkyl, silyl; X = halide) available for exploration of this area. To remedy this deficiency, reactions between ScX₃ (X = Cl and I) and 2 equiv of a variety of potassium cyclopentadienide reagents have been examined. This has provided, in good crystalline yield, the compounds [C₅H₃(SiMe₃)₂]₂ScI, [C₅Me₄(SiMe₃)]₂ScI, [C₅Me₄(SiMe₂<i>^t</i>Bu)]₂ScI, {[C₅H₄(SiMe₃)]₂Sc(μ-I)}₂, {[C₅H₄(Si<i>ⁱ</i>Pr₃)]₂Sc(μ-I)}₂, and {[C₅H₃(SiMe₃)₂]₂Sc(μ-Cl)}₂, each of which has been characterized by X-ray crystallography, elemental analysis, NMR spectroscopy (¹H, ¹³C{¹H}, ²⁹Si{¹H}, and ⁴⁵Sc), and infrared spectroscopy. The study has also revealed the facile cocrystallization of the oxide {[C₅H₃(SiMe₃)₂]₂Sc}₂(μ-O) and hydroxide {[C₅H₃(SiMe₃)₂]₂Sc(μ-OH)}₂ impurities from preparations of [C₅H₃(SiMe₃)₂]₂ScI using samples of ScI₃ that presumably contain an oxide contaminant.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 1","pages":"137–147 137–147"},"PeriodicalIF":2.5,"publicationDate":"2024-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143084998","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":"Importance of Ligand Fine-Tuning: Alkyne Metathesis with Molybdenum Alkylidyne Complexes Supported by Phenyl-tert-butoxysilanolate Ligands","authors":"Angelika Neitzel,&nbsp;Tobias Ludwig,&nbsp;Dirk Bockfeld,&nbsp;Thomas Bannenberg and Matthias Tamm*,&nbsp;","doi":"10.1021/acs.organomet.4c0043810.1021/acs.organomet.4c00438","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00438https://doi.org/10.1021/acs.organomet.4c00438","url":null,"abstract":"<p >The phenyl-<i>tert</i>-butoxysilanols Ph(<i>t</i>BuO)₂SiOH and Ph₂(<i>t</i>BuO)SiOH were prepared and used for the synthesis of the molybdenum 2,4,6-trimethylbenzylidyne complexes [MesC≡Mo{OSi(O<i>t</i>Bu)₂Ph}₃] (<b>1</b>) and [MesC≡Mo{OSi(O<i>t</i>Bu)Ph₂}₃] (<b>2</b>) from <i>mer-</i>[MesC≡MoBr₃(dme)] (dme = dimethoxyethane, Mes = 2,4,6-trimethylphenyl). The molecular structures of <b>1</b> and <b>2</b> were determined by X-ray diffraction analysis, revealing a secondary molybdenum–oxygen interaction and a chelating κ²<i>O</i>,<i>O</i>′ coordination mode of one of the siloxide ligands in the case of <b>1</b>. Treatment of <b>1</b> and <b>2</b> with an excess of 3-hexyne (EtC≡CEt) afforded the corresponding propylidyne (EtC≡Mo) complexes, which are in equilibrium with labile metallacyclobutadiene complexes as evidenced by variable-temperature NMR spectroscopy. Single crystals of [(Et₃C₃)Mo{OSi(O<i>t</i>Bu)Ph₂}₃] (<b>2-MCBD</b>) have been isolated at low temperature, providing a rare example of a crystallographically characterized molybdenacyclobutadiene. The alkylidyne complexes <b>1</b> (<i>n</i> = 1) and <b>2</b> (<i>n</i> = 2) complete the series of available alkyne metathesis (pre-)catalysts [RC≡Mo{OSi(O<i>t</i>Bu)_3–<i>n</i>Ph_<i>n</i>}₃] (<i>n</i> = 0–3), and their catalytic performance in the metathesis of internal and terminal alkynes was investigated and compared, if available, with the previous members of this series (<i>n</i> = 0, 3).</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 1","pages":"255–267 255–267"},"PeriodicalIF":2.5,"publicationDate":"2024-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.organomet.4c00438","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143085392","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":"Syntheses and Structures of Cationic Bis(gold) Cyclopentadienyl Complexes","authors":"Brady L. Slinger,&nbsp;Jack C. Malek and Ross A. Widenhoefer*,&nbsp;","doi":"10.1021/acs.organomet.4c0043610.1021/acs.organomet.4c00436","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00436https://doi.org/10.1021/acs.organomet.4c00436","url":null,"abstract":"<p >The reaction of (<b>P</b>)AuOTf [<b>P</b> = P(<i>t</i>-Bu)₂<i>o</i>-biphenyl] with the cyclopentadienyl lithium reagents C₅H₅Li, C₅H₄MeLi, and C₅HMe₄Li forms the corresponding gold η¹-cyclopentadienyl complexes (<b>P</b>)Au(η¹-C₅H₅) (<b>3a</b>), (<b>P</b>)Au(η¹-C₅H₄Me) (<b>3b</b>), and (<b>P</b>)Au(η¹-C₅HMe₄) (<b>3c</b>), respectively, in &gt;60% isolated yield. Treatment of complexes <b>3a</b> or <b>3b</b> with (<b>P</b>)AuNTf₂ forms the corresponding cationic bis(gold) cyclopentadienyl complexes <i>trans</i>-{[(<b>P</b>)Au]₂(η¹,η¹-cyclopentadien-1,3-yl)}⁺ NTf₂^– (<b>4a</b>) and <i>trans</i>-{[(<b>P</b>)Au]₂(η¹,η¹-methylcyclopentadien-1,3-yl)}⁺ NTf₂^– (<b>4b</b>), respectively, in near-quantitative yield, which were characterized in solution and by X-ray crystallography. Both <b>4a</b> and <b>4b</b> undergo migration of the gold atoms about the cyclopentadienyl ring, which is fast on the NMR time scale at −80 °C. In the solid state, the gold atoms of <b>4a</b> and <b>4b</b> are positioned on the opposite faces of the cyclopentadienyl ring above and below the C1 and C3 carbon atoms. The reaction of <b>3c</b> with (<b>P</b>)AuNTf₂ similarly forms the cationic bis(gold) tetramethylcyclopentadienyl complex {[(<b>P</b>)Au]₂(C₅HMe₄)}⁺ NTf₂^– (<b>4</b><b>c</b>) although the structure of this complex remains obscure. The binding affinity of mono(gold) complexes <b>3a</b>–<b>3c</b> toward exogenous (<b>P</b>)Au⁺ exceeds that of the corresponding unmetalated cyclopentadienes by more than 3 orders of magnitude. Protodeauration of bis(gold) complexes <b>4</b> with acetic acid at −80 °C is &gt;1500 times slower than the protodeauration of the corresponding monogold complexes <b>3</b> under identical conditions.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 1","pages":"224–235 224–235"},"PeriodicalIF":2.5,"publicationDate":"2024-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143085177","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":"A Lewis-Base-Supported Terminal Thorium Imido Metallocene [{η5-1,2,4-(Me3Si)3C5H2}2Th═N(p-tolyl)(bipy)]: Synthesis and Reactivity","authors":"Dongwei Wang,&nbsp;Yi Heng,&nbsp;Guohua Hou,&nbsp;Guofu Zi* and Marc D. Walter*,&nbsp;","doi":"10.1021/acs.organomet.4c0043110.1021/acs.organomet.4c00431","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00431https://doi.org/10.1021/acs.organomet.4c00431","url":null,"abstract":"&lt;p &gt;Addition of &lt;i&gt;p&lt;/i&gt;-tolylN&lt;sub&gt;3&lt;/sub&gt; to a toluene solution of thorium bipyridyl metallocene [{η&lt;sup&gt;5&lt;/sup&gt;-1,2,4-(Me&lt;sub&gt;3&lt;/sub&gt;Si)&lt;sub&gt;3&lt;/sub&gt;C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;2&lt;/sub&gt;}&lt;sub&gt;2&lt;/sub&gt;Th(bipy)] (&lt;b&gt;1&lt;/b&gt;) causes N&lt;sub&gt;2&lt;/sub&gt; evolution concomitant with the formation of Lewis-base-supported terminal thorium imido metallocene [{η&lt;sup&gt;5&lt;/sup&gt;-1,2,4-(Me&lt;sub&gt;3&lt;/sub&gt;Si)&lt;sub&gt;3&lt;/sub&gt;C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;2&lt;/sub&gt;}&lt;sub&gt;2&lt;/sub&gt;Th═N(&lt;i&gt;p&lt;/i&gt;-tolyl)(bipy)] (&lt;b&gt;2&lt;/b&gt;). Complex &lt;b&gt;2&lt;/b&gt; may initiate [2 + 2] or [2 + 1] cycloaddition reactions with internal alkynes PhC≡CPh and PhC≡CC≡CPh, thiobenzophenone Ph&lt;sub&gt;2&lt;/sub&gt;CS, organic nitriles such as PhCH&lt;sub&gt;2&lt;/sub&gt;CN and C&lt;sub&gt;6&lt;/sub&gt;H&lt;sub&gt;11&lt;/sub&gt;CN, and organic isonitriles such as 2,6-Me&lt;sub&gt;2&lt;/sub&gt;PhNC and C&lt;sub&gt;6&lt;/sub&gt;H&lt;sub&gt;11&lt;/sub&gt;NC, yielding the amido complex [{η&lt;sup&gt;5&lt;/sup&gt;-1-(CH&lt;sub&gt;2&lt;/sub&gt;Me&lt;sub&gt;2&lt;/sub&gt;Si)-2,4-(Me&lt;sub&gt;3&lt;/sub&gt;Si)&lt;sub&gt;2&lt;/sub&gt;C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;2&lt;/sub&gt;}{η&lt;sup&gt;5&lt;/sup&gt;-1,2,4-(Me&lt;sub&gt;3&lt;/sub&gt;Si)&lt;sub&gt;3&lt;/sub&gt;C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;2&lt;/sub&gt;}Th{N(&lt;i&gt;p&lt;/i&gt;-tolyl)C(Ph)═CH(Ph)}] (&lt;b&gt;3&lt;/b&gt;), five-membered heterocyclic complex [{η&lt;sup&gt;5&lt;/sup&gt;-1-(&lt;i&gt;p&lt;/i&gt;-tolyl)NC(Ph)═CHCC(Ph)CH&lt;sub&gt;2&lt;/sub&gt;SiMe&lt;sub&gt;2&lt;/sub&gt;-2,4-(Me&lt;sub&gt;3&lt;/sub&gt;Si)&lt;sub&gt;2&lt;/sub&gt;C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;2&lt;/sub&gt;}{η&lt;sup&gt;5&lt;/sup&gt;-1,2,4-(Me&lt;sub&gt;3&lt;/sub&gt;Si)&lt;sub&gt;3&lt;/sub&gt;C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;2&lt;/sub&gt;}Th] (&lt;b&gt;4&lt;/b&gt;), disulfido complex [{η&lt;sup&gt;5&lt;/sup&gt;-1,2,4-(Me&lt;sub&gt;3&lt;/sub&gt;Si)&lt;sub&gt;3&lt;/sub&gt;C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;2&lt;/sub&gt;}&lt;sub&gt;2&lt;/sub&gt;Th(S&lt;sub&gt;2&lt;/sub&gt;CPh&lt;sub&gt;2&lt;/sub&gt;)] (&lt;b&gt;6&lt;/b&gt;), iminato complexes [{η&lt;sup&gt;5&lt;/sup&gt;-1,2,4-(Me&lt;sub&gt;3&lt;/sub&gt;Si)&lt;sub&gt;3&lt;/sub&gt;C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;2&lt;/sub&gt;}&lt;sub&gt;2&lt;/sub&gt;Th{η&lt;sup&gt;3&lt;/sup&gt;-N(&lt;i&gt;p&lt;/i&gt;-tolyl)C(CH&lt;sub&gt;2&lt;/sub&gt;Ph)NH}(N═C═CHPh)] (&lt;b&gt;8&lt;/b&gt;) and [{η&lt;sup&gt;5&lt;/sup&gt;-1,2,4-(Me&lt;sub&gt;3&lt;/sub&gt;Si)&lt;sub&gt;3&lt;/sub&gt;C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;2&lt;/sub&gt;}&lt;sub&gt;2&lt;/sub&gt;Th{η&lt;sup&gt;3&lt;/sup&gt;-N(&lt;i&gt;p&lt;/i&gt;-tolyl)C(C&lt;sub&gt;6&lt;/sub&gt;H&lt;sub&gt;11&lt;/sub&gt;)NH}{N═C═C(CH&lt;sub&gt;2&lt;/sub&gt;)&lt;sub&gt;5&lt;/sub&gt;}] (&lt;b&gt;9&lt;/b&gt;), eight-membered heterocyclic complex [{η&lt;sup&gt;5&lt;/sup&gt;-1,2,4-(Me&lt;sub&gt;3&lt;/sub&gt;Si)&lt;sub&gt;3&lt;/sub&gt;C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;2&lt;/sub&gt;}&lt;sub&gt;2&lt;/sub&gt;Th{N(&lt;i&gt;p&lt;/i&gt;-tolyl)C(═N-2,6-Me&lt;sub&gt;2&lt;/sub&gt;Ph)C(H)═N(6-MePh-2-CH&lt;sub&gt;2&lt;/sub&gt;)}] (&lt;b&gt;11&lt;/b&gt;), and bis-amido complex [{η&lt;sup&gt;5&lt;/sup&gt;-1,2,4-(Me&lt;sub&gt;3&lt;/sub&gt;Si)&lt;sub&gt;3&lt;/sub&gt;C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;2&lt;/sub&gt;}&lt;sub&gt;2&lt;/sub&gt;Th{1-C&lt;sub&gt;6&lt;/sub&gt;H&lt;sub&gt;11&lt;/sub&gt;-2,2-(CH&lt;sub&gt;2&lt;/sub&gt;)&lt;sub&gt;5&lt;/sub&gt;-4-(&lt;i&gt;p&lt;/i&gt;-tolyl)N-5-C&lt;sub&gt;6&lt;/sub&gt;H&lt;sub&gt;11&lt;/sub&gt;N-(1,3-C&lt;sub&gt;4&lt;/sub&gt;HN&lt;sub&gt;2&lt;/sub&gt;)}] (&lt;b&gt;12&lt;/b&gt;), respectively. Moreover, with chlorosilane PhSiH&lt;sub&gt;2&lt;/sub&gt;Cl complex &lt;b&gt;2&lt;/b&gt; converts to thorium amido chloride complex [{η&lt;sup&gt;5&lt;/sup&gt;-1,2,4-(Me&lt;sub&gt;3&lt;/sub&gt;Si)&lt;sub&gt;3&lt;/sub&gt;C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;2&lt;/sub&gt;}&lt;sub&gt;2&lt;/sub&gt;Th(Cl){N(&lt;i&gt;p&lt;/i&gt;-tolyl)SiH&lt;sub&gt;2&lt;/sub&gt;Ph}] (&lt;b&gt;13&lt;/b&gt;), demonstrating that the thorium imido fragment may also act as a nucleophile. Nevertheless, complex &lt;b&gt;2&lt;/b&gt; may also initiate deprotonation reactions as shown by its reactivity with the imine (&lt;i&gt;p&lt;/i&gt;-tolyl)&lt;sub&gt;2&lt;/sub&gt;C═NH and thiazole to yield the amido–iminato complex [{η&lt;sup&gt;5&lt;/sup&gt;-1,2,4-(Me&lt;sub&gt;3&lt;/sub&gt;Si)&lt;sub&gt;3&lt;/sub&gt;C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;2&lt;/sub&gt;}&lt;sub&gt;","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 1","pages":"207–223 207–223"},"PeriodicalIF":2.5,"publicationDate":"2024-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.organomet.4c00431","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143085393","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 and Characterization of Sulfonium-Ylide-Stabilized Palladium Carbenes","authors":"Martin Stang,&nbsp; and ,&nbsp;Suzanne A. Blum*,&nbsp;","doi":"10.1021/acs.organomet.4c0041810.1021/acs.organomet.4c00418","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00418https://doi.org/10.1021/acs.organomet.4c00418","url":null,"abstract":"<p >Isolable sulfonium-ylide-stabilized palladium carbene complexes were synthesized through palladium(II)-induced cyclization of 1,2-alkynylarylsulfanes. X-ray crystallographic analysis characterized the maintenance of a palladium +2 oxidation state, with carbene-carbon–palladium bond lengths of 1.95 Å, indicating a partial double-bond character. These endocyclic sulfonium ylide carbenes represent the first characterized and/or isolable examples of this ligand class; such groups were previously proposed as reaction intermediates during cyclization–carbonylation reactions. A variety of palladium(II) complexes bearing sulfonium-ylide carbene ligands, with differing substituents, were synthesized, and the structure and stability of these complexes in solution were analyzed by ¹H and ¹³C NMR spectroscopy, revealing reversibility and a stability dependence on substituents. The chirality of the sulfur heteroatom and the overall properties these ligands provide a potential electronic and steric alternative to existing carbene ligands, which could facilitate the future development of complementary metal-based reactivity.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 1","pages":"169–178 169–178"},"PeriodicalIF":2.5,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143085079","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":"Defining the Speciation, Coordination Chemistry, and Lewis Acid Catalysis of Electronically Diverse Zinc Benzoates.","authors":"Lydia A Dunaway, Audrey G Davis, Victoria J Carter, Albert K Korir, Matthias Zeller, John J Kiernicki","doi":"10.1021/acs.organomet.4c00358","DOIUrl":"10.1021/acs.organomet.4c00358","url":null,"abstract":"<p><p>Zinc benzoates may provide an element of tunability that is not available to their ubiquitous acetate analogues. Unfortunately, the synthesis, speciation, and coordination chemistry of zinc benzoates are less developed than the acetates. In this study, we systematically investigate zinc benzoates to understand their propensity to favor solvate (Zn(O₂CAr)₂(L)₂) or cluster (Zn₄O(O₂CAr)₆) formation as well as their utility as metal complex precursors. The zinc benzoates were found to be Lewis acid catalysts comparable to their acetate counterparts for the formation of oxazolines from esters and amino alcohols.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 1","pages":"46-53"},"PeriodicalIF":2.5,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11734107/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142996254","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":"Isonitrile Insertion into Titanium Neopentylidene Alkyl Complexes Yields a Bifurcated Pathway to Form κ1-N-vinylamido or κ2-C,N-azaalleneyl Fragments","authors":"John B. Russell,&nbsp;Michael R. Gau,&nbsp;Patrick J. Carroll and Daniel J. Mindiola*,&nbsp;","doi":"10.1021/acs.organomet.4c0044210.1021/acs.organomet.4c00442","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00442https://doi.org/10.1021/acs.organomet.4c00442","url":null,"abstract":"<p >Three organometallic ligand scaffolds resulting from the insertion of 1-adamantyl isonitrile (C≡NAd; Ad = C₁₀H₁₅) into titanium neopentylidene complexes, [(PNP)Ti═CH<i>^t</i>Bu(X)] are described herein. Treatment of the titanium neopentylidene complex (PNP)Ti═CH<i>^t</i>Bu(OTf) (<b>1</b>-OTf, PNP^– = N[2-P<i>ⁱ</i>Pr₂-4-methylphenyl]₂^–, OTf = trifluoromethanesulfonate^–) with one equivalent of C≡NAd leads to the formation of a titanium η²-<b><i>C</i></b>,<b><i>N</i></b>-ketenimine, (PNP)Ti(η²-<b><i>C</i></b>,<b><i>N</i></b>-Ad<b>NC</b>CH<i>^t</i>Bu)(OTf) (<b>2</b>-OTf). However, when the titanium neopentylidene neopentyl complex (PNP)Ti═CH<i>^t</i>Bu(CH₂<i>^t</i>Bu) (<b>1</b>-Np) is added one equivalent of C≡NAd, a titanium neopentylidene κ¹-<b><i>N</i></b>-vinylamido complex (PNP)Ti═CH<i>^t</i>Bu(κ¹-<b><i>N</i></b>-Ad<b>N</b>CHCH<i>^t</i>Bu) (<b>3</b>) is formed. In contrast, the titanium neopentylidene methyl complex (PNP)Ti═CH<i>^t</i>Bu(CH₃) (<b>1</b>-Me) reacts with one equivalent of C≡NAd to produce a rare chelating κ²-<b><i>C</i></b>,<b><i>N</i></b>-azaalleneyl ligand, in the complex (PNP)Ti(κ²-<b><i>C</i></b>,<b><i>N</i></b>-Ad<b>N</b>C<b>C</b><i>^t</i>Bu) (<b>4</b>), with concurrent extrusion of methane. Independently, it is shown that treatment of <b>2</b>-OTf with one equivalent of neopentyl lithium (LiNp, Np^– = CH₂<i>^t</i>Bu) or a half equivalent of dimethyl magnesium (MgMe₂) smoothly forms complex <b>3</b> or <b>4</b>, respectively, and suggests that the η²-<b><i>C</i></b>,<b><i>N</i></b>-ketenimine ligand in <b>2</b>-OTf might be an intermediate ligand enroute to the neopentylidene κ¹-<b><i>N</i></b>-vinylamido or κ²-<b><i>C</i></b>,<b><i>N</i></b>-azaalleneyl complexes. Complexes <b>2</b>-OTf, <b>3</b> and <b>4</b> have been structurally and spectroscopically characterized and a proposed mechanism for the formation of complexes <b>3</b> and <b>4</b> is also described.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 1","pages":"279–288 279–288"},"PeriodicalIF":2.5,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143084850","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":"Defining the Speciation, Coordination Chemistry, and Lewis Acid Catalysis of Electronically Diverse Zinc Benzoates","authors":"Lydia A. Dunaway,&nbsp;Audrey G. Davis,&nbsp;Victoria J. Carter,&nbsp;Albert K. Korir,&nbsp;Matthias Zeller and John J. Kiernicki*,&nbsp;","doi":"10.1021/acs.organomet.4c0035810.1021/acs.organomet.4c00358","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00358https://doi.org/10.1021/acs.organomet.4c00358","url":null,"abstract":"<p >Zinc benzoates may provide an element of tunability that is not available to their ubiquitous acetate analogues. Unfortunately, the synthesis, speciation, and coordination chemistry of zinc benzoates are less developed than the acetates. In this study, we systematically investigate zinc benzoates to understand their propensity to favor solvate (Zn(O₂CAr)₂(L)₂) or cluster (Zn₄O(O₂CAr)₆) formation as well as their utility as metal complex precursors. The zinc benzoates were found to be Lewis acid catalysts comparable to their acetate counterparts for the formation of oxazolines from esters and amino alcohols.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 1","pages":"46–53 46–53"},"PeriodicalIF":2.5,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.organomet.4c00358","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143084854","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}