Highly regioselective anti-Markovnikov hydrosilylation of alkenes under mild conditions: Application of CCC-NHC pincer Rh complexes

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Organometallic Chemistry Pub Date : 2025-02-21 DOI:10.1016/j.jorganchem.2025.123579

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

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引用次数: 0

Abstract

A highly selective hydrosilylation of alkenes at room temperature, catalyzed by well-defined CCC–NHC pincer Rh complexes, [(^BuCⁱCⁱC^Bu)RhCl₂Py] (1), [(^BuCⁱCⁱC^Bu)RhCl₂(NHMe₂)] (2), [(^BuCⁱCⁱC^Bu)RhCl(µ-Cl)₂Rh(COD)] (3), and [(^BuCⁱCⁱC^Bu)RhCl(µ-Cl)]₂ (4), (^BuCⁱCⁱC^Bu = 2-(1,3-bis(N-butylimidazol-2-ylidene)phenylene) has been achieved. The catalytic system exhibits excellent regioselectivity, affording anti-Markovnikov products in moderate to excellent conversions (48–100 %). Precatalyst [(^BuCⁱCⁱC^Bu)RhCl(µ-Cl)₂Rh(COD)] (3) demonstrated the highest efficiency in promoting the anti-Markovnikov hydrosilylation of both aryl and alkyl alkenes with excellent selectivity (>99 %) when Et₃SiH is used as silane source in acetonitrile. Notably, the system tolerates straight chain alkyl alkenes without inducing isomerization, a commonly encountered limitation with many hydrosilylation catalytic systems.

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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.