Organometallics最新文献

{"title":"Metal–Ligand Cooperative Nitrile Activation Triggered by a Catalytic Amount of Weak Base","authors":"Stanislav Melnikov,&nbsp;Arie J. H. Multem,&nbsp;Pieter N. Oostenbrug,&nbsp;Martin Lutz,&nbsp;Daniël L. J. Broere","doi":"10.1021/acs.organomet.6c00104","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00104","url":null,"abstract":"<p>Nitriles are common functional groups in chemical buildingblocks,yet their direct conversion into diverse functional groups typicallyrequires forcing conditions due to the thermodynamic stability ofthe C≡N bond. Activation of nitriles through metal–ligandcooperativity (MLC) has emerged as a powerful strategy and typicallyinvolves the use of strong bases to generate a reactive complex featuringa dearomatized pincer ligand. Herein, we report a mononuclear rutheniumplatform supported by a 1,8-naphthyridine-based PNNP ligand that enablesnitrile activation via MLC using only catalytic amounts of the weakbase triethylamine. Combined experimental and computational mechanisticstudies reveal a mechanism proceeding via an initial endergonic liganddeprotonation that is followed by nitrile coordination, intramolecularnucleophilic attack and reprotonation of the resulting ketimido nitrogenby the conjugate acid of the base. In addition, we show that bimetallicanalogues undergo two concurrent metal–ligand cooperative activationevents of two acetonitrile molecules to form diastereomeric bis-ketiminecomplexes.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 17","pages":"2095–2103"},"PeriodicalIF":2.4,"publicationDate":"2026-09-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148958041","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":"Relative Stability of Metal Complexes with Various Diene Ligands: Experimental and Computational Study","authors":"Tatiana N. Petrushina,&nbsp;Nikita M. Ankudinov,&nbsp;Dmitry S. Perekalin","doi":"10.1021/acs.organomet.6c00215","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00215","url":null,"abstract":"<p>The binding strength of various dienes was establishedby NMR investigationof ligand exchange reactions in (diene)Rh(acac) complexes. The bindingaffinity decreases in the following order: tetraphenyl-cyclopentadienone&gt;1,5-cyclooctadiene &gt; norbornadiene &gt; tetrafluoro-benzobarrelene&gt;dimethyl-tetrafluoro-benzobarrelene &gt; bis(carboxymethyl)-norbornadiene≫ bis(<em>tert</em>-butyl)-1,4-quinone &gt;1,5-hexadiene&gt; bis(carboxymethyl)-2,2,2-bicyclooctadiene &gt; carvone &gt;1,4-benzoquinone.The experimental data were used to validate the B97-3c method, whichreproduces the observed trends with good accuracy (MAD = 1.1 kcalmol^–1) and can be applied for rapid prediction ofcoordination strength. Computational screening of metal–dienecombinations shows that the metal fragment has a larger impact onstability than the diene itself. In line with the Dewar–Chatt–Duncansonmodel, more electron-rich metals form more stable diene complexes.Electron-withdrawing cyclopentadienone and benzoquinone were identifiedas strong and effective ligands for further investigation in catalysis.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 17","pages":"2165–2169"},"PeriodicalIF":2.4,"publicationDate":"2026-09-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148958072","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: Synthesis and Structural Characterization of a Selenasila[2]ferrocenophane","authors":"Ryusei Hamano,&nbsp;Koh Sugamata,&nbsp;Takahiro Sasamori","doi":"10.1021/acs.organomet.6c00247","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00247","url":null,"abstract":"<p>Synthesis of a selenasila[2]ferrocenophane via intramolecularmethyltransfer from a methylselenide to a transient silylene or silylenoid,which is generated by the dehydrobromination of the correspondingferrocenyldibromosilane using lithium 2,2,6,6-tetramethylpiperidide,is described. The molecular geometry and structural parameters ofthe selenasila[2]ferrocenophane in the crystalline state were unequivocallydetermined by single-crystal X-ray diffraction analysis. The mildlystrained selenasila[2]ferrocenophane showed considerable stability,i.e., it did not undergo ring-opening polymerization even under high-temperatureconditions or upon treatment with <em>n</em>-BuLi. Chlorinationof the amino moiety in the selenasila[2]ferrocenophane quantitativelyafforded the corresponding chlorosilane while preserving the [2]ferrocenophaneframework, indicating its potential as a suitable building block fora variety of selenasila[2]ferrocenophanes.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 17","pages":"2091–2094"},"PeriodicalIF":2.4,"publicationDate":"2026-09-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148958057","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, Characterization, and Reactivity of “NONO” Calix[4]arene Zirconium Complexes","authors":"Matteo Cardoso,&nbsp;Frank Schaper","doi":"10.1021/acs.organomet.6c00175","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00175","url":null,"abstract":"<p>A series of zirconium(IV) complexeswith a bis(benzylamino)-<em>p-tert-</em>butylcalix[4]areneligand, LZrX₂, weresynthesized and structurally characterized via single-crystal X-raydiffraction and NMR. The obtained complexes proved to be unexpectedlysusceptible to protonation because of the low acidity of the ligand.A high flexibility of the calix[4]arene ligand allowed either distorted-octahedralcoordination or coordination numbers greater than 6. Complexes withdifferent ancillary ligands X showed modest activity and poor stereocontroltoward <em>rac</em>-lactide polymerization and proved to beunstable under polymerization conditions.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 17","pages":"2114–2131"},"PeriodicalIF":2.4,"publicationDate":"2026-09-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148958028","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, Characterization and Reactivity of Alkyl Iron(II) PCP Pincer Complexes","authors":"Matthias Käfer,&nbsp;Simon Gstöttner,&nbsp;Berthold Stöger,&nbsp;Antoine Dupé,&nbsp;Luis F. Veiros,&nbsp;Karl Kirchner","doi":"10.1021/acs.organomet.6c00256","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00256","url":null,"abstract":"<p>The syntheses and reactivity of a series of alkyl ironPCP pincercomplexes is described. The alkyl complexes of the type [Fe(PCP^CH2-<em>i</em>Pr)(R)(CO)₂] (R = CH₃, CH₂CH₃, CH₂CH₂CH₃, CH₂CH₂CH₂CH₃) are accessible in good yields (69–78%) by reduction of [Fe(PCP^CH2-<em>i</em>Pr)(Br)(CO)₂] with sodiumfollowed by oxidative addition of alkyl halides RX (X = Br or I).As alkyl complexes are typically prone to undergo migratory insertionreactions in the presence of potential strong ligands, [Fe(PCP^CH2-<em>i</em>Pr)(CH₂CH₂CH₃)(CO)₂] was treated with CO and CN<em>t</em>Bu affording the acyl complexes [Fe(PCP^CH2-<em>i</em>Pr)((C═O)–CH₂CH₂CH₃)(CO)₂] and [Fe(PCP^CH2-<em>i</em>Pr)(C═O)–CH₂CH₂CH₃)(CO)(CN<em>t</em>Bu)]in 98 and 91% yields. Upon treatment of [Fe(PCP^CH2-<em>i</em>Pr)((C═O)–CH₂CH₂CH₃)(CO)₂] with pinacolborane (HBpin) the hydridecomplex [Fe(PCP^CH2-<em>i</em>Pr)(H)(CO)₂] is obtained. When [Fe(PCP^CH2-<em>i</em>Pr)(CH₂CH₂CH₃)(CO)₂] is reactedwith an excess (4 equiv) of HBpin and SiH₂Ph₂, complexes [Fe(PCP^CH2-<em>i</em>Pr)(κ²<em>H,H</em>-H₂BPin)(CO)] and [Fe(PCP^CH2-<em>i</em>Pr)(SiHPh₂)(CO)], respectively,is formed. The first is a very labile complex readily liberating HBpinthereby undergoing decomposition to intractable materials. The latteris an unusually stable 16e^– complex. Finally, ina preliminary reactivity study [Fe(PCP^CH2-<em>i</em>Pr)(CO)₂(CH₂CH₂CH₃)]is demonstrated to be an active precatalyst for the hydroborationof nitriles with HBPin. The hydroboration reaction requires no additivesand proceeds with a catalyst loading of 2 mol % at 60 °C. Thereduction of nitriles and subsequent hydrolysis provide ready accessto aminomethylene units in organic molecules.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 17","pages":"2177–2184"},"PeriodicalIF":2.4,"publicationDate":"2026-09-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148958056","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 Comparisons of Pericyclic Reactions between Aminoborane (F3C)2BNMe2 and Substituted Butadienes: Dominance of the Diels–Alder [4 + 2] Cycloaddition","authors":"Thomas M. Gilbert","doi":"10.1021/acs.organomet.6c00204","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00204","url":null,"abstract":"<p>Different reactiontypes known to occur when (F₃C)₂BNMe₂, <strong>1</strong>, acts as an inorganic alkenewere studied computationally. Diels–Alder cycloadditions dominatethree other pericyclic reaction types by exhibiting lower activationbarriers and greater exothermicities. An upper bound of Δ<em>G</em>₂₉₈^‡ = 100 kJ mol^–1 appears appropriate for defining reactions that will occur experimentally.Substituting hydrogens with π-donor groups on the butadieneleads to lowered barriers, such that the model predicts a number ofplausible Diels–Alder reactions. Such substitution at the butadiene2-posiiton is predicted to lead to exclusive formation of rings withthe substituent on the carbon adjacent to the boron-bound carbon,a result caused by barrier differences traceable to electronic issues.The steric demand of the (F₃C)₂B moiety limitsplausible reactivity to cases where at least one CH₂ terminusis present on the butadiene. Thus, in reactions between <strong>1</strong> and a 1-substituted butadiene, the boron binds the CH₂ terminus and the nitrogen binds the CH(R) terminus. Diels–Alderreactions between <strong>1</strong> and 1,4-disubstituted butadienesare predicted to be implausible regardless of the electronic propertiesof the substituents.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 17","pages":"2140–2150"},"PeriodicalIF":2.4,"publicationDate":"2026-09-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148958059","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":"CpCo–Benzoquinone Complexes: Convenient CpCo(I) Precatalysts─Synthesis and Reactivity","authors":"Rahamdil Usman,&nbsp;Uwe Monkowius,&nbsp;Marko Hapke","doi":"10.1021/acs.organomet.6c00194","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00194","url":null,"abstract":"<p>We report an improved,convenient, and general synthesisof theair-stable complex CpCo(DQ) (DQ = duroquinone), originally describedby Schrauzer and Thyret in 1963, and applied this general protocolto the preparation of a series of related CpCo(<em>p</em>-benzoquinone)complexes with yields ranging from 35 to 96%. The complexes were characterizedby single-crystal X-ray diffraction, and the bonding characteristicswere compared to those of other CpCo–olefin complexes. Theircatalytic performance was evaluated in cyclotrimerization reactionsunder both thermal and photochemical conditions for the synthesisof pyridine and benzene derivatives.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 17","pages":"2132–2139"},"PeriodicalIF":2.4,"publicationDate":"2026-09-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148958060","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":"DFT Analysis of α-Bromoamide Activation Pathways in a Copper-Catalyzed Sonogashira C(sp3)-C(sp) Coupling with Phenylacetylene","authors":"Javier Heras-Domingo,&nbsp;Jesús Jover","doi":"10.1021/acs.organomet.6c00141","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00141","url":null,"abstract":"<p>The copper-catalyzed Sonogashira coupling of alkyl halideshasemerged as a powerful strategy for constructing C(sp³)-C(sp)bonds. This process often occurs through pathways that differ fromthe traditional two-electron model observed for classical Sonogashirareactions. In particular, the activation mode of the C(sp³)-Br bond in α-bromoamides remains mechanistically ambiguous,with both radical and nonradical pathways being proposed in literature.In this work, density functional theory calculations have been employedto investigate the mechanism of the copper-catalyzed coupling betweenphenylacetylene and an α-bromoamide as a model for the SonogashiraC(sp³)-C(sp) coupling. A comprehensive exploration of possibleC(sp³)-Br activation pathways, including single-electrontransfer, halogen atom transfer, and classical two-electron processes,has been carried out. The results support a mechanism involving initialphenylacetylene coordination and deprotonation at copper, followedby halogen atom transfer between the metal and the bromoamide, radicalrecombination, and reductive elimination as the most energeticallyfavorable pathway in toluene. Calculations suggest that solvent effectsmay have a substantial impact on the mechanistic landscape. In particular,polar solvents such as DMF have been found to reduce the reactionbarriers of pathways where charged species are formed, finally producinga different reaction sequence.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 17","pages":"2104–2113"},"PeriodicalIF":2.4,"publicationDate":"2026-09-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148958061","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":"Electroreduction of Activated Esters Catalyzed by a Manganese Complex","authors":"Kai-Thorben Kuessner,&nbsp;Nils Rotthowe,&nbsp;Max C. Holthausen,&nbsp;Nilay Hazari,&nbsp;Alexander J.M. Miller,&nbsp;Inke Siewert","doi":"10.1021/acs.organomet.6c00205","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00205","url":null,"abstract":"<p>Electrochemical hydrogenation(electrohydrogenation) using electronsand protons as H₂ surrogates offers a sustainable alternativeto conventional reduction methods. Herein, we report the manganese-catalyzedelectroreduction of activated esters employing a derivative of Mn(bpy)(CO)₃ (bpy = 2,2’-bipyridine) featuring a proton relay inthe ligand. Using low catalyst loadings (1 mol%), a range of fluorinatedesters were reduced to the corresponding alcohols under mild electrochemicalconditions. Experimental and quantum-chemical mechanistic studiesprovide an understanding of the reaction pathway. The key catalyticintermediate, a manganese hydride species, is generated by electrochemicalreduction of the precatalyst followed by protonation. Computationalanalysis indicates that hydrogenation proceeds via an outer-sphereH^–/H⁺ transfer pathway. These findingsexpand the scope of base-metal electrocatalytic hydrogenation to estersand provide insight into manganese-hydride-mediated electroreductionmechanisms.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 17","pages":"2151–2158"},"PeriodicalIF":2.4,"publicationDate":"2026-09-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148958043","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: Arene η6-Coordination to Chromium Tricarbonyl Promotes Cobalt-Catalyzed C–H Borylation of Electron-Rich Arenes","authors":"Richard D. Broene,&nbsp;Lauren Sablone,&nbsp;Tianyi Zhang,&nbsp;Carlota Odena,&nbsp;Alex M. Shimozono,&nbsp;Paul J. Chirik","doi":"10.1021/acs.organomet.6c00233","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00233","url":null,"abstract":"<p>The cobalt-catalyzedborylation of electron-rich arenes η⁶-coordinatedto [Cr(CO)₃] has been demonstratedusing the pyridine(dicarbene) pincer-supported dicobalt alkoxide (^iPrACNC)Co₂(^tBuO)₄ as theprecatalyst. Metal coordination accelerated the borylation of thearene by 20−200 fold, enabling reactivity with substrates thatwere otherwise sluggish or inactive for cobalt-catalyzed C–Hfunctionalization. The cobalt-catalyzed borylation of η⁶-coordinated electron-rich arenes proceeded at ambient temperaturein the absence of HBPin scavengers. Arene coordination to chromiumalso proved to be an effective strategy for reversal of the traditionalchemoselectivity of metal-catalyzed C(sp²)–H borylationas 2-fluorobiphenyl was exclusively functionalized at the more electron-richring.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 17","pages":"2078–2082"},"PeriodicalIF":2.4,"publicationDate":"2026-09-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148958017","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}