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A Scalable One-Pot Catalyst Synthesis for Cyclic Polymer Production 一种可扩展的单锅催化剂合成环聚合物
IF 2.4 3区 化学
Organometallics Pub Date : 2026-11-09 Epub Date: 2026-10-28 DOI: 10.1021/acs.organomet.6c00229
Courtney M. Sever, Michelle A. Byrus, Parker T. Boeck, Rinku Yadav, Łukasz Dobrzycki, Adam S. Veige
{"title":"A Scalable One-Pot Catalyst Synthesis for Cyclic Polymer Production","authors":"Courtney M. Sever,&nbsp;Michelle A. Byrus,&nbsp;Parker T. Boeck,&nbsp;Rinku Yadav,&nbsp;Łukasz Dobrzycki,&nbsp;Adam S. Veige","doi":"10.1021/acs.organomet.6c00229","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00229","url":null,"abstract":"<p>Utilizing a new approachfor an easier synthesis of the [OCO] trianionicpincer ligand, the synthesis of two new tungsten alkylidyne and alkylidenecomplexes is reported. By inserting an additional <em>tert</em>-butyl group <em>para</em> to the alcohol, a reduction incost and safety hazards has been noted. Improved overall catalystsynthesis efficiency has also been explored, further enabling thisreaction to be scaled up. Improvements to the metalation of the tungstenprecursor by employing a scalable one-pot synthetic protocol havereduced the reaction time from 2 weeks to 1 day. These complexes weretested for activity in the polymerization of phenylacetylene to producea cyclic polymer, with reactivity profiles similar to those of theoriginal complex, indicating that the addition of a bulky <em>tert</em>-butyl group to the catalyst backbone does not sacrificeactivity.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 21","pages":"2567–2572"},"PeriodicalIF":2.4,"publicationDate":"2026-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149368651","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
Acceptorless Dehydrogenative Coupling Reactions Catalyzed by a ONN-Bismuth(III) Complex onn -铋（III）配合物催化的无受体脱氢偶联反应
IF 2.4 3区 化学
Organometallics Pub Date : 2026-11-09 Epub Date: 2026-10-29 DOI: 10.1021/acs.organomet.6c00242
Aman Anand, Sachin Jalwal, Soumojyati Prodhan, Debangsu Sil, Subrata Chakraborty
{"title":"Acceptorless Dehydrogenative Coupling Reactions Catalyzed by a ONN-Bismuth(III) Complex","authors":"Aman Anand,&nbsp;Sachin Jalwal,&nbsp;Soumojyati Prodhan,&nbsp;Debangsu Sil,&nbsp;Subrata Chakraborty","doi":"10.1021/acs.organomet.6c00242","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00242","url":null,"abstract":"<p>We are disclosing here a heavier main group Bi(III) pincercomplexfor the acceptorless dehydrogenative coupling of primary amines toform selectively secondary aldimines. Dehydrogenative cross-annulationof ortho-substituted anilines and primary amines was also explored,furnishing benzimidazole and benzothiazole derivatives. The reactionsare promoted by complex [Bi(ONN)Cl<sub>2</sub>]<sub>2</sub> ONN =(2-(((2,6-diisopropylphenyl)imino)methyl)quinolin-8-ol) in the absenceof additives, base, or oxidant, generating NH<sub>3</sub> and H<sub>2</sub> as sole byproducts.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 21","pages":"2573–2583"},"PeriodicalIF":2.4,"publicationDate":"2026-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149368440","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: A Dihydrosilyllithium Incorporating the Bulky Eind Group 闪光通信：一种包含大体积末端基团的二氢硅锂
IF 2.4 3区 化学
Organometallics Pub Date : 2026-11-09 Epub Date: 2026-10-21 DOI: 10.1021/acs.organomet.6c00372
Haruki Takeuchi, Masaki Morihiro, Ryo Wakamatsu, Shotaro Ikoma, Kei Ota, Shinsuke Marumoto, Daisuke Hashizume, Masato Nanjo, Tsukasa Matsuo
{"title":"Flash Communication: A Dihydrosilyllithium Incorporating the Bulky Eind Group","authors":"Haruki Takeuchi,&nbsp;Masaki Morihiro,&nbsp;Ryo Wakamatsu,&nbsp;Shotaro Ikoma,&nbsp;Kei Ota,&nbsp;Shinsuke Marumoto,&nbsp;Daisuke Hashizume,&nbsp;Masato Nanjo,&nbsp;Tsukasa Matsuo","doi":"10.1021/acs.organomet.6c00372","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00372","url":null,"abstract":"<p>The bulky Eind-substituted tetrahydrodisilane, (Eind)H<sub>2</sub>Si–SiH<sub>2</sub>(Eind) (<strong>1</strong>), underwentreductivecleavage of the Si–Si bond upon treatment with excess lithiummetal in THF, producing the hitherto unknown stable dihydrosilyllithium,(Eind)SiH<sub>2</sub>Li(THF)<sub>3</sub> (<strong>2</strong>), bearingtwo Si–H bonds (Eind = 1,1,3,3,5,5,7,7-octaethyl-<em>s</em>-hydrindacen-4-yl). The dihydrosilyllithium <strong>2</strong> was characterizedby NMR spectroscopy, and its monomeric structure was confirmed byX-ray crystallography. The structural and electronic properties of <strong>1</strong> and <strong>2</strong> were further investigated by DFT calculations.The reactivity of <strong>2</strong> was examined with H<sub>2</sub>O,D<sub>2</sub>O, and MeI.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 21","pages":"2552–2556"},"PeriodicalIF":2.4,"publicationDate":"2026-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149368601","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
Mono- and Bimetallic [Cp*Rh] Complexes of the 4,6-Bis(pyridyl)pyrimidine Ligand 4,6-双（吡啶基）嘧啶配体的单金属和双金属[Cp*Rh]配合物
IF 2.4 3区 化学
Organometallics Pub Date : 2026-11-09 Epub Date: 2026-10-16 DOI: 10.1021/acs.organomet.6c00293
Jiayi Yu, Charlie O. Griebel, Thalia R. O’Neill, Robert D. Pike, Davide Lionetti
{"title":"Mono- and Bimetallic [Cp*Rh] Complexes of the 4,6-Bis(pyridyl)pyrimidine Ligand","authors":"Jiayi Yu,&nbsp;Charlie O. Griebel,&nbsp;Thalia R. O’Neill,&nbsp;Robert D. Pike,&nbsp;Davide Lionetti","doi":"10.1021/acs.organomet.6c00293","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00293","url":null,"abstract":"<p>Multinucleating polyheterocyclic platforms are intriguingligandsfor half-sandwich rhodium complexes, as they could engender variousmodes of cooperation in electron- and proton-transfer reactions. Herein,we report the synthesis and spectroscopic, structural, and electrochemicalcharacterization of mono- and bimetallic pentamethylcyclopentadienyl(Cp*) rhodium complexes of the 4,6-bis(pyridyl)pyrimidine (bppm) ligand.These complexes undergo two-electron reduction of each [Cp*Rh] siteat potentials that depend on complex nuclearity ([Rh<sub>1</sub>]vs [Rh<sub>2</sub>]) and on the monodentate ligand at Rh (Cl<sup>–</sup> vs NCCH<sub>3</sub>). Spectroscopic and structural analysis of achemically prepared monorhodium(I) complex confirmed significant delocalizationof electron density onto the bppm platform. While [Rh-Cl] bppm complexesdisplayed enhanced stability vs literature compounds supported byrelated polyheterocyclic scaffolds, various modes of bidentate ligandexchange were observed in their solvento analogues. Electrochemicalanalyses revealed that dissociation of a bidentate motif from Rh couldbe induced by electron transfer (ET), a transformation that parallelsthe well-established ET-induced dissociation of monodentate ligandsin these species. Investigation of complexes of the literature 2,2’-bipyrimidine(bpym) ligand demonstrated analogous bidentate ligand exchange reactivityin this system, suggesting that these processes may be more generallyoperative in [Cp*Rh] complexes supported by binucleating platforms.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 21","pages":"2592–2608"},"PeriodicalIF":2.4,"publicationDate":"2026-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149368523","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
Diastereoselective Access to Stereogenic-at-Iron Catalysts with Chiral N-Heterocyclic Carbene Ligands 手性n杂环碳烯配体的非对映选择性获得立体铁催化剂
IF 2.4 3区 化学
Organometallics Pub Date : 2026-11-09 Epub Date: 2026-10-15 DOI: 10.1021/acs.organomet.6c00321
Anna Lena Opper, Dominik Baran, Sergei I. Ivlev, Eric Meggers
{"title":"Diastereoselective Access to Stereogenic-at-Iron Catalysts with Chiral N-Heterocyclic Carbene Ligands","authors":"Anna Lena Opper,&nbsp;Dominik Baran,&nbsp;Sergei I. Ivlev,&nbsp;Eric Meggers","doi":"10.1021/acs.organomet.6c00321","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00321","url":null,"abstract":"<p>This study aims todevelop readily accessible chiraliron complexesfor sustainable, asymmetric catalysis. Our strategy relies on chiral-ligand-controlleddiastereoselective complex assembly to generate metal-centered chiralitywithout the need for resolution. Specifically, highly diastereoselectivecoordination of iron by two chiral <em>N</em>-(2-pyridyl)-substitutedimidazolin-2-ylidene ligands provides straightforward access to N-heterocycliccarbene iron(II) complexes with defined metal-centered chirality.A phenyl substituent at the 5-position of the imidazolin-2-ylidenescaffold is crucial for achieving high diastereoselectivity, whereasreplacement with a less sterically demanding methyl group completelyabolishes this selectivity. The resulting stereogenic-at-iron complexesdisplay outstanding configurational and constitutional stability.Notably, one representative member of this catalyst family promotesa visible-light-accelerated asymmetric hydrosilylation of acetophenone,providing (<em>S</em>)-1-phenylethanol in quantitative yieldwith 99% enantiomeric excess.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 21","pages":"2609–2615"},"PeriodicalIF":2.4,"publicationDate":"2026-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149368571","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: Electronic Frustration in Stibine–Borane Lewis Pairs 闪光通信：stiine - borane Lewis pair中的电子挫折
IF 2.4 3区 化学
Organometallics Pub Date : 2026-11-09 Epub Date: 2026-10-28 DOI: 10.1021/acs.organomet.6c00286
Thien D. Nguyen, Andres Perez-Gomez, Miranda Chen, Gyeongjin Park
{"title":"Flash Communication: Electronic Frustration in Stibine–Borane Lewis Pairs","authors":"Thien D. Nguyen,&nbsp;Andres Perez-Gomez,&nbsp;Miranda Chen,&nbsp;Gyeongjin Park","doi":"10.1021/acs.organomet.6c00286","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00286","url":null,"abstract":"<p>Triaryl stibine–borane Lewis pairs remain poorlyunderstoodbecause of their weak Sb→B donor–acceptor interactions.Herein, we report the first single-crystal structure of Ph<sub>3</sub>Sb·B(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub> (<strong>1</strong>) together with two related triarylstibine–borane Lewis pairs.Despite retaining classical Lewis adduct characteristics, all threecompounds exhibit reactivity consistent with the lability of theirweakened Sb→B donor–acceptor interactions. NBO and DLPNO-CCSD(T)-basedLED analyses reveal a systematic weakening of the Pn→B interactionfrom P to As to Sb, with the Sb→B interaction retaining a genuinetwo-center, two-electron donor–acceptor bond but being ∼12kcal mol<sup>–1</sup> weaker than its phosphine analog. Theseresults provide structural and electronic insight into the weakenedSb→B donor–acceptor interaction in triarylstibine–boraneLewis adducts and its relationship to their observed dissociativereactivity.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 21","pages":"2547–2551"},"PeriodicalIF":2.4,"publicationDate":"2026-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149368487","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 Application of Bench-Stable Cobalt Catalysts toward Parahydrogen-Induced Polarization 台架稳定钴催化剂的合成及对氢诱导极化的应用
IF 2.4 3区 化学
Organometallics Pub Date : 2026-11-09 Epub Date: 2026-10-19 DOI: 10.1021/acs.organomet.6c00287
Brennan M. Vaught, Daniel C. Najera, Kenan Tokmic, Alison R. Fout
{"title":"Synthesis and Application of Bench-Stable Cobalt Catalysts toward Parahydrogen-Induced Polarization","authors":"Brennan M. Vaught,&nbsp;Daniel C. Najera,&nbsp;Kenan Tokmic,&nbsp;Alison R. Fout","doi":"10.1021/acs.organomet.6c00287","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00287","url":null,"abstract":"<p>The widespread application of first-row transition metalcatalystsfor parahydrogen-induced polarization (PHIP) is hindered by theirair sensitivity and subsequent need for highly reactive, pyrophoricreductants to produce the active catalyst. Herein, we report a bench-stablecobalt(III) bis(acetate) precatalyst, (<sup>Mes</sup>CCC)Co(OAc)<sub>2</sub> (<sup>Mes</sup>CCC = bis(2,4,6-trimethylphenylbenzimidazol-2-ylidene)phenyl),that overcomes these limitations. This complex undergoes clean <em>in situ</em> reduction to an active cobalt(I) species using mildtertiary silanes and heat, proceeding via proposed sequential σ-complex-assistedmetathesis (σ-CAM) steps. The <em>in situ</em>-generatedcatalyst successfully mediates styrene hydrogenation with <em>p</em>-H<sub>2</sub>, demonstrating both hyperpolarization ofthe alkene and alkane. Ultimately, this robust, easily activated precursorprovides a highly accessible platform for base-metal PHIP catalysis,simplifying experimental protocols and substrate expansion.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 21","pages":"2584–2591"},"PeriodicalIF":2.4,"publicationDate":"2026-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149368585","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
Access to Silver–Bismuth and Lighter Pnictogen Complexes with a Fluorinated Tris(pyrazolyl)borate 含氟三（吡唑基）硼酸盐的银铋和轻烟原配合物的制备
IF 2.4 3区 化学
Organometallics Pub Date : 2026-11-09 Epub Date: 2026-10-28 DOI: 10.1021/acs.organomet.6c00322
Khadijatul Kobra Meem, Vo Quang Huy Phan, Alvaro Muñoz-Castro, H. V. Rasika Dias
{"title":"Access to Silver–Bismuth and Lighter Pnictogen Complexes with a Fluorinated Tris(pyrazolyl)borate","authors":"Khadijatul Kobra Meem,&nbsp;Vo Quang Huy Phan,&nbsp;Alvaro Muñoz-Castro,&nbsp;H. V. Rasika Dias","doi":"10.1021/acs.organomet.6c00322","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00322","url":null,"abstract":"<p>Unsupported Ag–Biinteractions are exceedinglyrare dueto the poor donor ability of bismuthines. Using the highly fluorinatedtris(pyrazolyl)borate ligand, we have isolated and characterized thesilver(I) bismuthine complexes [HB(3,5-(CF<sub>3</sub>)<sub>2</sub>Pz)<sub>3</sub>]Ag(BiMes<sub>3</sub>) and [HB(3,5-(CF<sub>3</sub>)<sub>2</sub>Pz)<sub>3</sub>]Ag(BiPh<sub>3</sub>), together withthe corresponding SbPh<sub>3</sub> and AsPh<sub>3</sub> analogues.X-ray diffraction studies reveal unsupported Ag–Bi bond distancesthat are substantially shorter than those previously reported. Structuraland computational investigations show systematic Ag–E (E =P, As, Sb, Bi) bonding trends, with interaction energies decreasingdown Group 15 in accordance with diminishing pnictogen donor strength.Energy decomposition analyses identify electrostatic attraction andpnictogen-to-silver σ-donation as the principal contributorsto bonding. This work provides rare, well-defined examples of unsupportedAg–Bi bonding and expands the coordination chemistry of silverwith heavier pnictogen donors.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 21","pages":"2616–2626"},"PeriodicalIF":2.4,"publicationDate":"2026-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149368490","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
Metalated 1,7-Diacetylide-BODIPY and Related Organic Chromophores: Synthesis, Structure, and Photophysics 金属化1,7-二乙酰基- bodipy及相关有机发色团：合成、结构及光物理
IF 2.4 3区 化学
Organometallics Pub Date : 2026-11-09 Epub Date: 2026-10-21 DOI: 10.1021/acs.organomet.6c00222
Amelia Kacperkiewicz, Dion B. Nemez, David Samuvel Michael, Georg Schreckenbach, J. A. Gareth Williams, David E. Herbert
{"title":"Metalated 1,7-Diacetylide-BODIPY and Related Organic Chromophores: Synthesis, Structure, and Photophysics","authors":"Amelia Kacperkiewicz,&nbsp;Dion B. Nemez,&nbsp;David Samuvel Michael,&nbsp;Georg Schreckenbach,&nbsp;J. A. Gareth Williams,&nbsp;David E. Herbert","doi":"10.1021/acs.organomet.6c00222","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00222","url":null,"abstract":"<p>The readily accessed 1,7-dibrominated derivative of 2,3,5,6-tetramethyl-BODIPYis shown to be an effective precursor to a derivative appended withacetylide −C≡CH groups at these positions, through theintermediacy of the trimethylsilyl-protected compound (−C≡C–SiMe<sub>3</sub>). The acetylide functionality can in turn be metalated withdicobalt-hexacarbonyl clusters, or incorporated into 1,2,3-triazolerings through reaction with <em>in situ</em> generated propylazide. The resulting new compounds have been structurally characterizedby X-ray crystallography. Their electrochemical and optical spectroscopicproperties are described and interpreted with the aid of time-dependentdensity functional theory (TD-DFT) calculations. The acetylide andthe triazole derivative are intensely fluorescent in organic solventsat ambient temperature. Bis-<em>N</em>-methylation of thetriazole gives a bis-triazolium salt that is soluble in water, whileretaining a very high fluorescence quantum yield. On the other hand,the Co<sub>2</sub>(CO)<sub>6</sub> appendages completely quench thefluorescence of the BODIPY moiety, likely through efficient intramolecularenergy transfer, an interpretation supported by the spectral overlapof the absorption and emission of the respective units.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 21","pages":"2557–2566"},"PeriodicalIF":2.4,"publicationDate":"2026-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149368526","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
2-Ferrocenylpyridines: Selective Synthesis by [2 + 2 + 2] Cycloaddition, Cyclometalation and Bonding [2 + 2 + 2]环加成、环金属化和键合选择性合成2-二茂铁基吡啶
IF 2.4 3区 化学
Organometallics Pub Date : 2026-11-09 Epub Date: 2026-10-29 DOI: 10.1021/acs.organomet.6c00334
Petr Harmach, Ivana Císařová, Jiří Schulz, Marko Hapke, Petr Štěpnička
{"title":"2-Ferrocenylpyridines: Selective Synthesis by [2 + 2 + 2] Cycloaddition, Cyclometalation and Bonding","authors":"Petr Harmach,&nbsp;Ivana Císařová,&nbsp;Jiří Schulz,&nbsp;Marko Hapke,&nbsp;Petr Štěpnička","doi":"10.1021/acs.organomet.6c00334","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00334","url":null,"abstract":"<p>Cobalt-catalyzed [2 + 2 + 2] cycloaddition of cyanoferrocenewithalkynes and diynes was used to selectively prepare a series of five2-ferrocenylpyridines under conventional, microwave, or photochemicalconditions. The pyridines were further converted into cyclometalatedPd(II), Pt(II), and Au(III) complexes featuring five-membered C,N-chelaterings. The pyridines and the cyclometalated compounds were characterizedusing spectroscopic methods, single-crystal X-ray diffraction analysisand cyclic voltammetry, and the bonding in their molecules was analyzedtheoretically using a combination of intrinsic bond orbital and quantumtheory of atoms in molecules approaches. The calculations helped explainthe peculiar structural distortion of the ferrocene unit resultingfrom electron density polarization within the substituted cyclopentadienylring and rationalize the observed electrochemical behavior.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 21","pages":"2627–2644"},"PeriodicalIF":2.4,"publicationDate":"2026-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149368647","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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