Formation and Reactivity of a Hexahydridosilicate [SiH6](2-) Coordinated by a Macrocycle-Supported Strontium Cation - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Angewandte Chemie International Edition Année : 2022

Formation and Reactivity of a Hexahydridosilicate [SiH6](2-) Coordinated by a Macrocycle-Supported Strontium Cation

Résumé

The cationic benzyl complex [(Me(4)TACD)Sr(CH2Ph)][A] (Me(4)TACD=1,4,7,10-tetramethyltetraazacyclododecane; A=B(C6H3-3,5-Me-2)(4)) reacted with two equivalents of phenylsilane to give the bridging hexahydridosilicate complex [(Me(4)TACD)(2)Sr-2(thf)(4)(mu-kappa(3) : kappa(3)-SiH6)][A](2) (3 a). Rapid phenyl exchange between phenylsilane molecules is assumed to generate monosilane SiH4 that is trapped by two strontium hydride cations [(Me(4)TACD)SrH(thf)(x)](+). Complex 3 a decomposed in THF at room temperature to give the terminal silanide complex [(Me(4)TACD)Sr(SiH3)(thf)(2)][A], with release of H-2. Upon reaction with a weak Bronsted acid, CO2, and 1,3,5,7-cyclooctatetraene SiH4 was released. The reaction of a 1 : 2 mixture of cationic benzyl and neutral dibenzyl complex with phenylsilane gave the trinuclear silanide complex [(Me(4)TACD)(3)Sr-3(mu(2)-H)(3)(mu(3)-SiH3)(2)][A], while (n)OctSiH(3) led to the trinuclear (n-octyl)pentahydridosilicate complex [(Me(4)TACD)(3)Sr-3(mu(2)-H)(3)(mu(3)-SiH(5)(n)Oct)][A].

Dates et versions

hal-03714657 , version 1 (05-07-2022)

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Thomas Hoellerhage, Priyabrata Ghana, Thomas P. Spaniol, Ambre Carpentier, Laurent Maron, et al.. Formation and Reactivity of a Hexahydridosilicate [SiH6](2-) Coordinated by a Macrocycle-Supported Strontium Cation. Angewandte Chemie International Edition, 2022, 61 (10), ⟨10.1002/anie.202115379⟩. ⟨hal-03714657⟩
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