Organometallics最新文献

筛选
英文 中文
Structure, Bonding, and Electrochemical Studies of Osmaboranes Comprising Planar B4 Ring 构成平面B4环的锇硼烷的结构、键合和电化学研究
IF 2.4 3区 化学
Organometallics Pub Date : 2026-08-24 Epub Date: 2026-08-05 DOI: 10.1021/acs.organomet.6c00170
Sampad Shyamal, Debipada Chatterjee, Shivankan Mishra, Sangeetha Nunavath, Sundargopal Ghosh
{"title":"Structure, Bonding, and Electrochemical Studies of Osmaboranes Comprising Planar B4 Ring","authors":"Sampad Shyamal,&nbsp;Debipada Chatterjee,&nbsp;Shivankan Mishra,&nbsp;Sangeetha Nunavath,&nbsp;Sundargopal Ghosh","doi":"10.1021/acs.organomet.6c00170","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00170","url":null,"abstract":"<p>An osmaborane featuring a planar [B<sub>4</sub>H<sub>8</sub>]<sup>2–</sup> ring has been synthesized and structurallycharacterized.Prolonged thermolysis of the intermediate generated from the reactionof [Os(PPh<sub>3</sub>)<sub>3</sub>Cl<sub>2</sub>] (<strong>1</strong>) with dppf [dppf = 1,1′-Bis(diphenylphosphino) ferrocene]in the presence of excess [BH<sub>3</sub>·THF] afforded [Os(dppf)H<sub>2</sub>(η<sup>4</sup>–B<sub>4</sub>H<sub>8</sub>)] (<strong>2</strong>) along with [H(dppf)OsB<sub>5</sub>H<sub>10</sub>] (<strong>3</strong>) and [{HOs(dppf)}<sub>2</sub>(μ-H)B<sub>4</sub>H<sub>7</sub>] (<strong>4</strong>). Complex <strong>2</strong> contains a planar[B<sub>4</sub>H<sub>8</sub>]<sup>2–</sup> ring and is an osmiumanalog of pentaborane(9). Complex <strong>3</strong> is the osmium analogof hexaborane(10). On the other hand, complex <strong>4</strong> adoptsa <em>nido</em> monocapped square pyramidal geometry whichis structurally analogous to [{HOs(PPh<sub>3</sub>)<sub>2</sub>}<sub>2</sub>(μ-H)B<sub>4</sub>H<sub>7</sub>] (<strong>5</strong>), obtainedfrom the prolonged thermolysis of [Os(PPh<sub>3</sub>)<sub>3</sub>Cl<sub>2</sub>] (<strong>1</strong>) with excess of [BH<sub>3</sub>·THF]alongside the earlier reported [Os(PPh<sub>3</sub>)<sub>2</sub>H<sub>2</sub>(η<sup>4</sup>–B<sub>4</sub>H<sub>8</sub>)] (<strong>I</strong>) and [H(PPh<sub>3</sub>)<sub>2</sub>OsB<sub>5</sub>H<sub>10</sub>] (<strong>II</strong>). Surprisingly, no analogous productswere obtained using dppm [dppm = 1,2-bis(diphenylphosphino)methane]and dppe [dppe = 1,2-bis(diphenylphosphino)ethane]. All synthesizedmolecules were characterized through multinuclear NMR and IR spectroscopyand mass spectrometry. Single-crystal X-ray diffraction analyses ofclusters <strong>2</strong> and <strong>5</strong> established their solid-statestructures, while theoretical investigations elucidated the bondingin <strong>2</strong>. In addition, comparative electrochemical studiesof <strong>2</strong> and <strong>I</strong> were carried out to examine electroniccommunication and to assess the influence of the redox-active dppfligand on the electronic properties of the complex.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 16","pages":"1960–1968"},"PeriodicalIF":2.4,"publicationDate":"2026-08-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148810287","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
Reactivity of Bestmann’s Ylide, Ph3PCOO, with the Actinides: Observation of An–C Bond Insertion or κ-O Coordination Bestmann 's Ylide Ph3PCOO与锕系元素的反应性:An-C键插入或κ-O配位的观察
IF 2.4 3区 化学
Organometallics Pub Date : 2026-08-24 Epub Date: 2026-08-13 DOI: 10.1021/acs.organomet.6c00251
Gabriella S. Godinho, Qien Feng, Guang Wu, Trevor W. Hayton
{"title":"Reactivity of Bestmann’s Ylide, Ph3PCOO, with the Actinides: Observation of An–C Bond Insertion or κ-O Coordination","authors":"Gabriella S. Godinho,&nbsp;Qien Feng,&nbsp;Guang Wu,&nbsp;Trevor W. Hayton","doi":"10.1021/acs.organomet.6c00251","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00251","url":null,"abstract":"<p>Reaction of 2 equiv of Bestmann’s ylide, Ph<sub>3</sub>PCCO,with the Th(IV) metallacycle, [Th{<em>N</em>(R)(SiMe<sub>2</sub><em>C</em>H<sub>2</sub>)}(NR<sub>2</sub>)<sub>2</sub>] (R= SiMe<sub>3</sub>), results in formation of [Th{<em>N</em>(R)(SiMe<sub>2</sub>CHC(C(H)PPh<sub>3</sub>)<em>O</em>}(NR<sub>2</sub>)<sub>2</sub>(<em>O</em>CCPPh<sub>3</sub>)] (<strong>1</strong>). The first equivalent of phosphoranylideneketene insertsinto the Th–C bond, which is accompanied by a 1,3-H shift toform an η<sup>3</sup>-oxy-allyl fragment. The second equivalentof Ph<sub>3</sub>PCCO coordinates to the metal center in a κ-Ofashion. Reaction of [AnCl(NR<sub>2</sub>)<sub>3</sub>] (An = U, Th)with 1 equiv of Ph<sub>3</sub>PCCO results in the formation of [AnCl(NR<sub>2</sub>)<sub>3</sub>(<em>O</em>CCPPh<sub>3</sub>)] (An =U, <strong>2</strong>; Th, <strong>3</strong>) in good yields. In both cases,the phosphoranylideneketene coordinates to the metal center in a κ-Ofashion. Complexes <strong>1</strong>, <strong>2</strong>, and <strong>3</strong> were characterized by NMR and IR spectroscopies and X-ray crystallography.They represent the first reported actinide phosphoranylideneketenecomplexes.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 16","pages":"1883–1887"},"PeriodicalIF":2.4,"publicationDate":"2026-08-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148810314","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
Iridium and Ruthenium Complexes Bearing Uracil-Functionalized N-Heterocyclic Carbenes: Synthesis and Catalytic Activity in the Reduction of NAD+ 含尿嘧啶功能化n杂环碳烯的铱钌配合物的合成及其还原NAD+的催化活性
IF 2.4 3区 化学
Organometallics Pub Date : 2026-08-10 Epub Date: 2026-07-27 DOI: 10.1021/acs.organomet.6c00157
Giulia Francescato, Catarina S. Roque, André Taborda, Giulia Romeo, Clara Gomes, Lígia O. Martins, Ana Petronilho
{"title":"Iridium and Ruthenium Complexes Bearing Uracil-Functionalized N-Heterocyclic Carbenes: Synthesis and Catalytic Activity in the Reduction of NAD+","authors":"Giulia Francescato,&nbsp;Catarina S. Roque,&nbsp;André Taborda,&nbsp;Giulia Romeo,&nbsp;Clara Gomes,&nbsp;Lígia O. Martins,&nbsp;Ana Petronilho","doi":"10.1021/acs.organomet.6c00157","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00157","url":null,"abstract":"<p>The synthesis of iridium and ruthenium complexes bearinga uracil-derivedN-heterocyclic carbene (NHC) ligand is reported herein, and theirapplication for the reduction of NAD+ is described. The synthesisemploys two different synthetic pathways, yielding both abnormal andnormal NHC complexes, with iridium demonstrating a strong preferencefor the abnormal coordination mode. The catalytic performance of thecomplexes was evaluated for the reduction of NAD<sup>+</sup> to NADHusing formic acid as a proton source. The iridium complexes significantlyoutperform their ruthenium analogs, which are essentially inactiveand show signs of instability. Among the iridium complexes, normalNHC <strong>5</strong> exhibits superior catalytic activity, robustness,and reduced susceptibility to substrate inhibition compared with itsabnormal counterpart.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 15","pages":"1808–1817"},"PeriodicalIF":2.4,"publicationDate":"2026-08-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148698893","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
Reduction Chemistry of Bis(cyclopentadienyl) Scandium Iodides with Isocyanides: Sc(II) Complexes, Isocyanide Coupling, and Aquo Adducts 双(环戊二烯基)碘化钪与异氰酸盐的还原化学:Sc(II)配合物、异氰酸盐偶联和水基加合物
IF 2.4 3区 化学
Organometallics Pub Date : 2026-08-10 Epub Date: 2026-07-30 DOI: 10.1021/acs.organomet.6c00181
Jonah P. Stiel, Joshua D. Queen, Joseph W. Ziller, William J. Evans
{"title":"Reduction Chemistry of Bis(cyclopentadienyl) Scandium Iodides with Isocyanides: Sc(II) Complexes, Isocyanide Coupling, and Aquo Adducts","authors":"Jonah P. Stiel,&nbsp;Joshua D. Queen,&nbsp;Joseph W. Ziller,&nbsp;William J. Evans","doi":"10.1021/acs.organomet.6c00181","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00181","url":null,"abstract":"<p>To better define scandium(II) reduction chemistry andto studyligand effects on the hyperfine coupling to <sup>45</sup>Sc in theEPR spectra of Sc(II) complexes, which could be useful in the designof qubits based on nd<sup>1</sup> electronic configurations, the reductionof bis(cyclopentadienyl) scandium(III) iodide complexes in the presenceof isocyanide ligands has been examined. Both pentamethyl- and tetramethylcyclopentadienylcomplexes have been examined with isocyanides CNR, where R = 2,6-dimethylphenyl(Xylyl), 1-naphthyl (Naph), and 2,6-diisopropylphenyl (Dipp). Thesynthesis and structures of the isocyanide adducts of Sc(III) metalloceneiodides, Cp<sup>x</sup><sub>2</sub>ScI(CNR) [Cp<sup>x</sup> = C<sub>5</sub>Me<sub>5</sub> (Cp*) and C<sub>5</sub>Me<sub>4</sub>H (Cp<sup>tet</sup>)] are described as well as EPR data on the Sc(II) productsformed by reduction of Cp<sup>x</sup><sub>2</sub>ScI in the presenceof CNR. A more direct synthetic route to the Sc(II) complex, Cp*<sub>2</sub>Sc(CNXylyl)<sub>2</sub>, is reported. New Sc(III) complexesobtained from these reactions are also described including [Cp<sup>tet</sup><sub>2</sub>Sc(μ-CN)]<sub>4</sub> which is the firstcrystallographically characterized Sc complex containing (CN)<sup>1–</sup> cyanide ligands, as well as products with two andthree coupled isocyanides, Cp<sup>tet</sup><sub>2</sub>Sc(XylylNCCNXylyl)ScCp<sup>tet</sup><sub>2</sub>, Cp<sup>tet</sup><sub>2</sub>Sc(C<sub>27</sub>N<sub>3</sub>H<sub>28</sub>), and Cp<sup>x</sup><sub>2</sub>Sc(C<sub>33</sub>N<sub>3</sub>H<sub>22</sub>). In addition, the [Cp*<sub>2</sub>Sc(CNXylyl)<sub>2</sub>]<sup>1+</sup> cation was isolated as the(BPh<sub>4</sub>)<sup>1–</sup> salt for comparison with theSc(II) analog, Cp*<sub>2</sub>Sc(CNXylyl)<sub>2</sub>, and the unexpectedorganometallic aquo adducts, [Cp<sup>tet</sup><sub>2</sub>Sc(H<sub>2</sub>O)<sub>2</sub>][I][THF] and Cp<sup>tet</sup><sub>2</sub>Sc(OH)(H<sub>2</sub>O), were fortuitously crystallized.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 15","pages":"1842–1852"},"PeriodicalIF":2.4,"publicationDate":"2026-08-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148698950","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
Bis(phosphinite)-Supported Palladium Catalysts for Homogeneous Dehydrogenation of Formic Acid 双(亚磷酸酯)负载钯催化剂对甲酸均相脱氢的催化作用
IF 2.4 3区 化学
Organometallics Pub Date : 2026-08-10 Epub Date: 2026-07-28 DOI: 10.1021/acs.organomet.6c00135
N. Sai Kumar, Anubendu Adhikary, Hairong Guan
{"title":"Bis(phosphinite)-Supported Palladium Catalysts for Homogeneous Dehydrogenation of Formic Acid","authors":"N. Sai Kumar,&nbsp;Anubendu Adhikary,&nbsp;Hairong Guan","doi":"10.1021/acs.organomet.6c00135","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00135","url":null,"abstract":"<p>Palladium-catalyzeddehydrogenation of formic acid underhomogeneousconditions is rare. In most cases, decomposition of palladium complexesis observed under the reaction conditions. In this study, bis(phosphinite)-supportedpalladium(II) complexes, {2,6-(R<sub>2</sub>PO)<sub>2</sub>C<sub>6</sub>H<sub>3</sub>}PdX [R = <sup><em>i</em></sup>Pr, <sup><em>t</em></sup>Bu; X = H (<strong>1a</strong>–<strong>b</strong>),OCHO (<strong>2a</strong>–<strong>b</strong>)], were examined for catalyticformic acid dehydrogenation (FAD). Their derivative complexes, {2,6-(R<sub>2</sub>PO)<sub>2</sub>C<sub>6</sub>H<sub>3</sub>}PdCH<sub>3</sub> (<strong>3a</strong>–<strong>b</strong>), were found to be precatalysts.During catalysis, complex degradation was observed; however, by optimizingthe reaction conditions (80 °C, ethanol), a homogeneous and additive-freeprocedure for FAD was achieved. Alcohols and dihydrogen were identifiedas the possible sources of catalyst decomposition. Mechanistic investigationsreveal that the protonation of {2,6-(R<sub>2</sub>PO)<sub>2</sub>C<sub>6</sub>H<sub>3</sub>}PdH (<strong>1a</strong>–<strong>b</strong>)is both kinetically and thermodynamically favored, which drives FADwhile suppressing catalyst degradation pathways. It was found thatthe sterically crowded {2,6-(<sup><em>t</em></sup>Bu<sub>2</sub>PO)<sub>2</sub>C<sub>6</sub>H<sub>3</sub>}PdCH<sub>3</sub> (<strong>3b</strong>) is a more effective catalyst compared to {2,6-(<sup><em>i</em></sup>Pr<sub>2</sub>PO)<sub>2</sub>C<sub>6</sub>H<sub>3</sub>}PdCH<sub>3</sub> (<strong>3a</strong>). Experimental data show thatCO<sub>2</sub> elimination, the rate-limiting step of the catalyticcycle, occurs more rapidly from {2,6-(<sup><em>t</em></sup>Bu<sub>2</sub>PO)<sub>2</sub>C<sub>6</sub>H<sub>3</sub>}PdOCHO (<strong>2b</strong>) than from {2,6-(<sup><em>i</em></sup>Pr<sub>2</sub>PO)<sub>2</sub>C<sub>6</sub>H<sub>3</sub>}PdOCHO (<strong>2a</strong>), thereby accelerating the overall reaction rate.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 15","pages":"1795–1807"},"PeriodicalIF":2.4,"publicationDate":"2026-08-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148698932","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 of High-Purity Dialkylzinc Compounds for Coordinative Chain Transfer Polymerization 配位链转移聚合用高纯二烷基锌化合物的合成
IF 2.4 3区 化学
Organometallics Pub Date : 2026-08-10 Epub Date: 2026-07-21 DOI: 10.1021/acs.organomet.6c00182
Ju Yong Park, Hye In Seo, Sangdeok Seo, Wonbean Yang, Go Eun Han, Junseong Lee, Bun Yeoul Lee
{"title":"Synthesis of High-Purity Dialkylzinc Compounds for Coordinative Chain Transfer Polymerization","authors":"Ju Yong Park,&nbsp;Hye In Seo,&nbsp;Sangdeok Seo,&nbsp;Wonbean Yang,&nbsp;Go Eun Han,&nbsp;Junseong Lee,&nbsp;Bun Yeoul Lee","doi":"10.1021/acs.organomet.6c00182","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00182","url":null,"abstract":"<p>R<sub>2</sub>Zn compounds prepared by the conventional method (reactionof 2 eq RMgCl with ZnCl<sub>2</sub> in Et<sub>2</sub>O, followed byfiltration to remove MgCl<sub>2</sub>) are often unsuitable for certainorganic and polymer syntheses─particularly coordinative chaintransfer polymerization (CCTP)─due to residual impurities.Herein, we disclose a convenient, safe, scalable, and cost-effectivemethod for the preparation of high-purity R<sub>2</sub>Zn that performseffectively in CCTP. In this approach, RMgCl, generated in Et<sub>2</sub>O or the less hazardous (CH<sub>3</sub>O)<sub>2</sub>CH<sub>2</sub>, are reacted with ZnCl<sub>2</sub>. Subsequent removal ofthe ether solvent affords a residue containing both the desired R<sub>2</sub>Zn product and dried MgCl<sub>2</sub> byproduct. The driedMgCl<sub>2</sub> acts as an impurity scrubber during the hexane extractionstep, enabling isolation of highly pure R<sub>2</sub>Zn compounds.Using this method, [CH<sub>2</sub>═C(R)C<sub>6</sub>H<sub>4</sub>(CH<sub>2</sub>)<sub><em>x</em></sub>]<sub>2</sub>Zn [<strong>1</strong> (<em>x</em> = 3, R = H); <strong>2</strong> (<em>x</em> = 3, R = Me); <strong>3</strong> (<em>x</em> = 2,R = H); <strong>4</strong> (<em>x</em> = 2, R = Me)] was efficientlysynthesized. These reagents enabled the formation of high yields ofCH<sub>2</sub>═C(R)C<sub>6</sub>H<sub>4</sub>(CH<sub>2</sub>)<sub><em>x</em></sub>-[(CH(R)CH<sub>2</sub>)]<em><sub>n</sub></em>-Zn-[(CH<sub>2</sub>CH(R))]<em><sub>n</sub></em>-(CH<sub>2</sub>)<sub><em>x</em></sub>C<sub>6</sub>H<sub>4</sub>C(R)═CH<sub>2</sub> in CCTP. GPC, <sup>1</sup>H NMR,and rotational rheology analyses of the resulting polymers indicatethat a fraction of the styrene units in <strong>1</strong> and <strong>3</strong> is incorporated into the polymer backbone, leading to higher-molecular-weightmaterials with long-chain branching.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 15","pages":"1832–1841"},"PeriodicalIF":2.4,"publicationDate":"2026-08-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148698887","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: Intramolecular Chalcogen Bonding as a Driver of Diaryltelluride Oxidation by o-Chloranil 闪光通讯:分子内的氯键驱动邻氯胺氧化二芳基碲化物
IF 2.4 3区 化学
Organometallics Pub Date : 2026-08-10 Epub Date: 2026-07-17 DOI: 10.1021/acs.organomet.6c00178
You Jiang, Chenggang Jiang, François P. Gabbaï
{"title":"Flash Communication: Intramolecular Chalcogen Bonding as a Driver of Diaryltelluride Oxidation by o-Chloranil","authors":"You Jiang,&nbsp;Chenggang Jiang,&nbsp;François P. Gabbaï","doi":"10.1021/acs.organomet.6c00178","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00178","url":null,"abstract":"<p>Given potential ramificationsin catalysis, exploringredox cyclingat heavy main group centers is attracting renewed interest. In thiscontext, this study explores how chalcogen bonding interactions caninfluence the oxidative addition of <em>o</em>-chloranil tothe Te(II) center of diaryltellurides. Using a series of diaryltelluridesfunctionalized by <em>ortho</em>-methylene-dimethylamino or-methyl ether functionalities, we show that the formation of a chalcogenbond between the donor atom and the tellurium center drives the oxidationreaction, as confirmed by the isolation and structural characterizationof the corresponding Te(IV) monocatecholates. Furthermore, this studyalso shows that these tetravalent tellurium derivatives react withan additional equivalent of <em>o</em>-chloranil to affordhexachloro-dibenzo[1,4]dioxine-2,3-dione, a known compound, and thecorresponding Te(IV) dichlorides. Lastly, this work also documentsthe facile reductions of the Te(IV) dichlorides into their Te(II)diaryl precursors using dithiothreitol or DTT.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 15","pages":"1764–1769"},"PeriodicalIF":2.4,"publicationDate":"2026-08-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148698912","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
Organometallic Chemistry Beyond the Transition Metals 过渡金属以外的有机金属化学
IF 2.4 3区 化学
Organometallics Pub Date : 2026-08-10 Epub Date: 2026-05-29 DOI: 10.1021/acs.organomet.6c00122
Manuel Alcarazo, David C. Powers, Alexander T. Radosevich
{"title":"Organometallic Chemistry Beyond the Transition Metals","authors":"Manuel Alcarazo,&nbsp;David C. Powers,&nbsp;Alexander T. Radosevich","doi":"10.1021/acs.organomet.6c00122","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00122","url":null,"abstract":"","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 15","pages":"1755–1758"},"PeriodicalIF":2.4,"publicationDate":"2026-08-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148698915","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
Bimetallic C–H Activation in Methanol Dehydrogenation: Metal–Metal Cooperativity in a Naphthyl-Bridged Diiridium Pyridine Diimine Complex 甲醇脱氢中的双金属C-H活化:萘桥接二铱吡啶二亚胺配合物中的金属-金属协同性
IF 2.4 3区 化学
Organometallics Pub Date : 2026-08-10 Epub Date: 2026-07-21 DOI: 10.1021/acs.organomet.6c00102
Thomas Marx, Wiebke Dammann, Peter Burger
{"title":"Bimetallic C–H Activation in Methanol Dehydrogenation: Metal–Metal Cooperativity in a Naphthyl-Bridged Diiridium Pyridine Diimine Complex","authors":"Thomas Marx,&nbsp;Wiebke Dammann,&nbsp;Peter Burger","doi":"10.1021/acs.organomet.6c00102","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00102","url":null,"abstract":"<p>Dinuclear iridium complexes supported by a 1,8-naphthyl-bridgedpyridine diimine (PDI) ligand exhibit pronounced metal–metalcooperativity (MMC) in the acceptorless dehydrogenation of methanol.Whereas the corresponding mononuclear analogues are inert, the diiridiummethoxido intermediate undergoes clean conversion to a carbonyl–dihydridecomplex via cooperative C–H activation of a coordinated formaldehydefragment. Structural characterization by X-ray crystallography andmultinuclear NMR spectroscopy, combined with isotopic labeling, establishthe methoxide origin of the carbonyl ligand. Variable-temperatureNMR studies reveal dynamic hydride exchange consistent with a low-barrierη<sup>2</sup>-H<sub>2</sub> transition state. Computationalanalysis identifies two competing pathways─a Meerwein-Ponndorf-Verley-typeroute and an organometallic α-C–H activation pathway─withcomparable activation barriers (∼26 kcal·mol<sup>–1</sup>). Both involve transient Ir–Ir distance contraction.These results demonstrate that metal–metal proximity enablescooperative bond activation inaccessible to mononuclear analoguesand provide design principles for bimetallic alcohol dehydrogenation.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 15","pages":"1781–1794"},"PeriodicalIF":2.4,"publicationDate":"2026-08-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148698879","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: Reactivity of Bis(phosphine) Ligands with Dicobalt Octacarbonyl 闪光通讯:双(膦)配体与八羰基二钴的反应性
IF 2.4 3区 化学
Organometallics Pub Date : 2026-08-10 Epub Date: 2026-07-17 DOI: 10.1021/acs.organomet.6c00176
Rowan M. Bailey, Tsz-Kan Ma, Dominykas Dautoras, Benedek Stadler, Álvaro García-Romero, Andrew J. P. White, James A. Bull, Mark R. Crimmin, Philip W. Miller
{"title":"Flash Communication: Reactivity of Bis(phosphine) Ligands with Dicobalt Octacarbonyl","authors":"Rowan M. Bailey,&nbsp;Tsz-Kan Ma,&nbsp;Dominykas Dautoras,&nbsp;Benedek Stadler,&nbsp;Álvaro García-Romero,&nbsp;Andrew J. P. White,&nbsp;James A. Bull,&nbsp;Mark R. Crimmin,&nbsp;Philip W. Miller","doi":"10.1021/acs.organomet.6c00176","DOIUrl":"https://doi.org/10.1021/acs.organomet.6c00176","url":null,"abstract":"<p>A series of bis(phosphine)cobalt carbonyl complexeswere preparedand investigated <em>in situ</em> using cyclic voltammetry, <sup>1</sup>H, <sup>31</sup>P, and <sup>59</sup>Co NMR spectroscopy (includingDOSY), and IR spectroscopy. X-ray diffraction analysis on isolatedsingle crystals confirmed that complex speciation was highly dependenton the nature of the bis(phosphine) and ligand-to-metal stoichiometry.Reactions of [Co<sub>2</sub>(CO)<sub>8</sub>] with 1,2-bis(dicyclohexylphosphino)ethane(DCyPE) and 1,2-bis(diphenylphosphino)benzene (DPPBz) led todisproportionation of the precursor, affording cationic <em>κ</em><sup>2</sup>-Co(I) bis(phosphine) complexes with Co(−I) tetracarbonylcobaltate counteranions. In contrast, ferrocenyl bis(phosphine) ligands1,1′-bis(diphenylphosphino)ferrocene (DPPF), 1,1′-bis(di-isopropylphosphino)ferrocene(D<sup>i</sup>PrPF), and 1,1′-bis(dicyclohexylphosphino)ferrocene(DCyPF), displayed different reactivity. D<sup>i</sup>PrPF and DCyPFappeared to form polymeric species at 1:1 ligand-to-metal ratios butfavored the formation of discrete neutral dinuclear complexes of thetype [(μ<sup>2</sup>-L)Co<sub>2</sub>(CO)<sub>6</sub>] when0.5 equiv of ligand was employed. Reaction of [Co<sub>2</sub>(CO)<sub>8</sub>] with DPPF yielded a significantly larger molecular assembly.Single-crystal X-ray diffraction revealed an unprecedented metallocyclicstructure comprising six cobalt tricarbonyl centers interconnectedby four bridging DPPF ligands.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"45 15","pages":"1759–1763"},"PeriodicalIF":2.4,"publicationDate":"2026-08-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148693693","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
0
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
确定
请完成安全验证×
相关产品
×
本文献相关产品
联系我们:info@booksci.cn Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。 Copyright © 2023 布克学术 All rights reserved.
京ICP备2023020795号-1
ghs 京公网安备 11010802042870号
Book学术文献互助
Book学术文献互助群
群 号:604180095
Book学术官方微信
小红书