Dehydrogenative silylation of vinylarenes with Et3SiH catalyzed by mixed valent CCC-NHC Rh(III)/Rh(I) pincer complex

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Journal of Organometallic Chemistry Pub Date : 2025-05-01 Epub Date: 2025-03-01 DOI:10.1016/j.jorganchem.2025.123578

Enock D. Amoateng, Bruno Donnadieu, Evans Fosu, T. Keith Hollis

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Abstract

Selective dehydrogenative silylation of vinylarenes with tertiary silanes catalyzed by well-defined CCC–NHC pincer Rh complexes has been developed. The CCC–NHC pincer Rh precatalysts [(^BuCⁱCⁱC^Bu)RhCl(µ-Cl)₂Rh(COD)] (7), [(^BuCⁱCⁱC^Bu)RhCl(µ-Cl)]₂ (8), [(^BuCⁱCⁱC^Bu)RhCl₂(NHMe₂)] (9), and [(^BuCⁱCⁱC^Bu)RhCl₂Py] (10), (^BuCⁱCⁱC^Bu = 2-((1,3-bis(N-butylimidazol-2-ylidene)phenylene) that were evaluated were all found to promote the dehydrogenative silylation of vinylarenes with Et₃SiH to selectively form the corresponding (E)-alkenylsilane under solvent-free conditions. The most active precatalyst was the novel mixed valent Rh(III)/Rh(I) complex, [(^BuCⁱCⁱC^Bu)RhCl(µ-Cl)₂Rh(COD)] (7). The catalytic system displays wide substrate scope. Electron rich and electron deficient vinylarenes were well tolerated affording the corresponding alkenylsilanes in good yields (65–86 %). Preliminary mechanistic investigations indicated that the Rh(III) center was responsible for the catalytic performance.

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混合价CCC-NHC Rh(III)/Rh(I)钳形配合物催化乙烯烯与Et3SiH的脱氢硅化反应

研究了用定义良好的CCC-NHC钳形Rh配合物催化乙烯烯与叔硅烷的选择性脱氢硅基化反应。所评价的CCC-NHC螯合Rh预催化剂[(BuCiCiCBu)RhCl（µ- cl）2Rh(COD)](7)、[(BuCiCiCBu)RhCl（µ- cl）]2(8)、[(BuCiCiCBu)RhCl2(NHMe2)](9)、[(BuCiCiCBu)RhCl2Py]（10）、(BuCiCiCBu = 2-(（1,3-二（n -丁基咪唑-2-乙基）苯基）]均能促进乙烯基芳烃与Et3SiH的脱氢硅基化反应，在无溶剂条件下选择性生成相应的(E)-烯基硅烷。催化活性最高的预催化剂为新型混合价Rh(III)/Rh(I)配合物[(BuCiCiCBu)RhCl（µ-Cl）2Rh(COD)](7)。富电子乙烯烯和缺电子乙烯烯耐受性好，产率高（65 - 86%）。初步机理研究表明，Rh（III）中心对催化性能起主要作用。

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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.