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

Year: 2025

Type: article

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 [( Bu C i C i C Bu )RhCl(µ-Cl) 2 Rh(COD)] ( 7 ), [( Bu C i C i C Bu )RhCl(µ-Cl)] 2 ( 8 ), [( Bu C i C i C Bu )RhCl 2 (NHMe 2 )] ( 9 ), and [( Bu C i C i C Bu )RhCl 2 Py] ( 10 ), ( Bu C i C i C Bu = 2-((1,3-bis(N-butylimidazol-2-ylidene)phenylene) that were evaluated were all found to promote the dehydrogenative silylation of vinylarenes with Et 3 SiH 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, [( Bu C i C i C Bu )RhCl(µ-Cl) 2 Rh(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.

Source: Journal of Organometallic Chemistry

DOI: 10.1016/j.jorganchem.2025.123578

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

Institution: Mississippi State University

Language: English

Topic: N-Heterocyclic Carbenes in Organic and Inorganic Chemistry

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: hybrid

Estimated APC paid: $3,970