Hydrosilylation of Olefins Activated on Highly Lewis-Acidic Calcium Cation.

Grochowska-Tatarczak, M; Koteras, K; Kazimierczuk, K; Malinowski, P J

Grochowska-Tatarczak, M; Koteras, K; Kazimierczuk, K; Malinowski, P J.

Afiliación

Grochowska-Tatarczak M; Centre of New Technologies, University of Warsaw, Banacha 2c, 02-093, Warsaw, Poland.
Koteras K; Centre of New Technologies, University of Warsaw, Banacha 2c, 02-093, Warsaw, Poland.
Kazimierczuk K; Centre of New Technologies, University of Warsaw, Banacha 2c, 02-093, Warsaw, Poland.
Malinowski PJ; Centre of New Technologies, University of Warsaw, Banacha 2c, 02-093, Warsaw, Poland.

Chemistry ; 30(45): e202401322, 2024 Aug 12.

Article en En | MEDLINE | ID: mdl-38660917

ABSTRACT

ABSTRACT

The report introduces simple yet highly reactive calcium salt, Ca[Al(ORF)4]2 (RF=C(CF3)3), 1, which effectively catalyses olefin hydrosilylation through an unusual mechanism involving the activation of the alkene molecule. Upon dissolution in o-difluorobenzene (oDFB), 1 forms a highly Lewis acidic [Ca(oDFB)6]2+ complex. Our DFT calculations reveal that fluoride ion affinity is comparable to SbF5. Reactivity tests show that it effectively catalyses the hydrosilylation of olefins with high regioselectivity, also in reactions involving sterically demanding substrates like (iPr)3SiH or tetrasubstituted olefins. Experimental and computational results point to the mechanism where the olefin molecule forms a complex with Ca2+, which significantly facilitates the attack of H-SiR3 on the C=C double bond.

Palabras clave

Calcium; Lewis acid; hydrosilylation; olefin; weakly coordinating anion

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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: Chemistry Asunto de la revista: QUIMICA Año: 2024 Tipo del documento: Article País de afiliación: Polonia Pais de publicación: Alemania

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