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

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Organometallic Chemistry Pub Date : 2024-12-30 DOI:10.1016/j.jorganchem.2024.123497

Naoya Noguchi, Toshiro Takao

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引用次数: 0

Abstract

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.

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来源期刊

Journal of Organometallic Chemistry 化学-无机化学与核化学

CiteScore

4.40

自引率

8.70%

发文量

221

审稿时长

36 days

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.