{"title":"用二钌双（μ-乙炔）配合物与三维金属羰基反应制备了一系列含桥接乙炔配体的杂双金属配合物：在Ru2Fe位点上的烷基炔-烷基炔偶联反应","authors":"Naoya Noguchi, Toshiro Takao","doi":"10.1016/j.jorganchem.2024.123497","DOIUrl":null,"url":null,"abstract":"<div><div>Diruthenium bis(μ-ethylidyne) complex [(Cp*Ru)<sub>2</sub>(μ-CMe)<sub>2</sub>] (<strong>1</strong>) reacts smoothly with metal carbonyls of group 6–9 3d metals to afford heterobimetallic tri- and tetranuclear complexes. While bis(ethylidyne) complexes [(Cp*Ru)<sub>2</sub>(μ-CMe)(μ<sub>3</sub>-CMe)(μ-CO)<sub>2</sub>{Cr(CO)<sub>3</sub>}] (<strong>2</strong>) and [(Cp*Ru)<sub>2</sub>(μ<sub>3</sub>-CMe)<sub>2</sub>(μ-CO){Fe(CO)<sub>3</sub>}] (<strong>4</strong>) were obtained by the reaction of <strong>1</strong> with [Cr(CO)<sub>6</sub>] and [Fe(CO)<sub>5</sub>], respectively, the reaction with [Mn<sub>2</sub>(CO)<sub>10</sub>] yielded μ-vinylidene−μ<sub>3</sub>-ethylidyne complex [(Cp*Ru)<sub>2</sub>(μ-C=CH<sub>2</sub>)(μ<sub>3</sub>-CMe)(μ-CO)<sub>2</sub>{Mn(CO)<sub>3</sub>}] (<strong>3</strong>) accompanied by the abstraction of a methyl proton by [Mn(CO)<sub>5</sub>]<sup>•</sup>. By the reaction with an excess amount of [Co<sub>2</sub>(CO)<sub>8</sub>], tetranuclear bis(μ<sub>3</sub>-ethylidyne) complex [(Cp*Ru)<sub>2</sub>(μ<sub>3</sub>-CMe)<sub>2</sub>(μ-CO){Co(CO)<sub>2</sub>}<sub>2</sub>] (<strong>6</strong>) was exclusively obtained. These reactions implied that the delocalized π-electrons in the [Ru<sub>2</sub>C<sub>2</sub>] core of <strong>1</strong> were used to construct the heterometallic skeleton with unsaturated organometallic species. Although complexes <strong>2</strong> and <strong>3</strong> underwent fragmentation upon gentle heating, <strong>4</strong> reacted with CO at 60 °C to yield μ<sub>3</sub>-η<sup>2</sup>(||)-butyne complex [(Cp*Ru)<sub>2</sub>(μ<sub>3</sub>-η<sup>2</sup>(||)-MeCCMe)(μ<sub>3</sub>-CO)(μ-CO){Fe(CO)<sub>3</sub>}] (<strong>5</strong>) via the alkylidyne−alkylidyne coupling. The density functional theory (DFT) calculations suggested that the C−C bond formation occurs via the intermediate containing μ- and μ<sub>3</sub>-ethylidyne ligands followed by the migration of the <em>m</em>-ethylidyne ligand across the Ru<sub>2</sub>Fe plane.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1026 ","pages":"Article 123497"},"PeriodicalIF":2.7000,"publicationDate":"2025-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Preparation of a series of heterobimetallic complexes containing bridging ethylidyne ligands by the reaction of diruthenium Bis(μ-ethylidyne) complex with 3d metal carbonyls: Alkylidyne−alkylidyne coupling reaction at the Ru2Fe site\",\"authors\":\"Naoya Noguchi, Toshiro Takao\",\"doi\":\"10.1016/j.jorganchem.2024.123497\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>Diruthenium bis(μ-ethylidyne) complex [(Cp*Ru)<sub>2</sub>(μ-CMe)<sub>2</sub>] (<strong>1</strong>) reacts smoothly with metal carbonyls of group 6–9 3d metals to afford heterobimetallic tri- and tetranuclear complexes. While bis(ethylidyne) complexes [(Cp*Ru)<sub>2</sub>(μ-CMe)(μ<sub>3</sub>-CMe)(μ-CO)<sub>2</sub>{Cr(CO)<sub>3</sub>}] (<strong>2</strong>) and [(Cp*Ru)<sub>2</sub>(μ<sub>3</sub>-CMe)<sub>2</sub>(μ-CO){Fe(CO)<sub>3</sub>}] (<strong>4</strong>) were obtained by the reaction of <strong>1</strong> with [Cr(CO)<sub>6</sub>] and [Fe(CO)<sub>5</sub>], respectively, the reaction with [Mn<sub>2</sub>(CO)<sub>10</sub>] yielded μ-vinylidene−μ<sub>3</sub>-ethylidyne complex [(Cp*Ru)<sub>2</sub>(μ-C=CH<sub>2</sub>)(μ<sub>3</sub>-CMe)(μ-CO)<sub>2</sub>{Mn(CO)<sub>3</sub>}] (<strong>3</strong>) accompanied by the abstraction of a methyl proton by [Mn(CO)<sub>5</sub>]<sup>•</sup>. By the reaction with an excess amount of [Co<sub>2</sub>(CO)<sub>8</sub>], tetranuclear bis(μ<sub>3</sub>-ethylidyne) complex [(Cp*Ru)<sub>2</sub>(μ<sub>3</sub>-CMe)<sub>2</sub>(μ-CO){Co(CO)<sub>2</sub>}<sub>2</sub>] (<strong>6</strong>) was exclusively obtained. These reactions implied that the delocalized π-electrons in the [Ru<sub>2</sub>C<sub>2</sub>] core of <strong>1</strong> were used to construct the heterometallic skeleton with unsaturated organometallic species. Although complexes <strong>2</strong> and <strong>3</strong> underwent fragmentation upon gentle heating, <strong>4</strong> reacted with CO at 60 °C to yield μ<sub>3</sub>-η<sup>2</sup>(||)-butyne complex [(Cp*Ru)<sub>2</sub>(μ<sub>3</sub>-η<sup>2</sup>(||)-MeCCMe)(μ<sub>3</sub>-CO)(μ-CO){Fe(CO)<sub>3</sub>}] (<strong>5</strong>) via the alkylidyne−alkylidyne coupling. The density functional theory (DFT) calculations suggested that the C−C bond formation occurs via the intermediate containing μ- and μ<sub>3</sub>-ethylidyne ligands followed by the migration of the <em>m</em>-ethylidyne ligand across the Ru<sub>2</sub>Fe plane.</div></div>\",\"PeriodicalId\":374,\"journal\":{\"name\":\"Journal of Organometallic Chemistry\",\"volume\":\"1026 \",\"pages\":\"Article 123497\"},\"PeriodicalIF\":2.7000,\"publicationDate\":\"2025-02-15\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Organometallic Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0022328X24004923\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"2024/12/30 0:00:00\",\"PubModel\":\"Epub\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Organometallic Chemistry","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0022328X24004923","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2024/12/30 0:00:00","PubModel":"Epub","JCR":"Q3","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Preparation of a series of heterobimetallic complexes containing bridging ethylidyne ligands by the reaction of diruthenium Bis(μ-ethylidyne) complex with 3d metal carbonyls: Alkylidyne−alkylidyne coupling reaction at the Ru2Fe site
Diruthenium bis(μ-ethylidyne) complex [(Cp*Ru)2(μ-CMe)2] (1) reacts smoothly with metal carbonyls of group 6–9 3d metals to afford heterobimetallic tri- and tetranuclear complexes. While bis(ethylidyne) complexes [(Cp*Ru)2(μ-CMe)(μ3-CMe)(μ-CO)2{Cr(CO)3}] (2) and [(Cp*Ru)2(μ3-CMe)2(μ-CO){Fe(CO)3}] (4) were obtained by the reaction of 1 with [Cr(CO)6] and [Fe(CO)5], respectively, the reaction with [Mn2(CO)10] yielded μ-vinylidene−μ3-ethylidyne complex [(Cp*Ru)2(μ-C=CH2)(μ3-CMe)(μ-CO)2{Mn(CO)3}] (3) accompanied by the abstraction of a methyl proton by [Mn(CO)5]•. By the reaction with an excess amount of [Co2(CO)8], tetranuclear bis(μ3-ethylidyne) complex [(Cp*Ru)2(μ3-CMe)2(μ-CO){Co(CO)2}2] (6) was exclusively obtained. These reactions implied that the delocalized π-electrons in the [Ru2C2] core of 1 were used to construct the heterometallic skeleton with unsaturated organometallic species. Although complexes 2 and 3 underwent fragmentation upon gentle heating, 4 reacted with CO at 60 °C to yield μ3-η2(||)-butyne complex [(Cp*Ru)2(μ3-η2(||)-MeCCMe)(μ3-CO)(μ-CO){Fe(CO)3}] (5) via the alkylidyne−alkylidyne coupling. The density functional theory (DFT) calculations suggested that the C−C bond formation occurs via the intermediate containing μ- and μ3-ethylidyne ligands followed by the migration of the m-ethylidyne ligand across the Ru2Fe plane.
期刊介绍：
The Journal of Organometallic Chemistry targets original papers dealing with theoretical aspects, structural chemistry, synthesis, physical and chemical properties (including reaction mechanisms), and practical applications of organometallic compounds.
Organometallic compounds are defined as compounds that contain metal - carbon bonds. The term metal includes all alkali and alkaline earth metals, all transition metals and the lanthanides and actinides in the Periodic Table. Metalloids including the elements in Group 13 and the heavier members of the Groups 14 - 16 are also included. The term chemistry includes syntheses, characterizations and reaction chemistry of all such compounds. Research reports based on use of organometallic complexes in bioorganometallic chemistry, medicine, material sciences, homogeneous catalysis and energy conversion are also welcome.
The scope of the journal has been enlarged to encompass important research on organometallic complexes in bioorganometallic chemistry and material sciences, and of heavier main group elements in organometallic chemistry. The journal also publishes review articles, short communications and notes.
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