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

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Abstract

The cationic benzyl complex [(Me4TACD)Sr(CH2Ph)][A] (Me4TACD=1,4,7,10-tetramethyltetraazacyclododecane; A=B(C6H3-3,5-Me2)4) reacted with two equivalents of phenylsilane to give the bridging hexahydridosilicate complex [(Me4TACD)2Sr2(thf)4(μ-κ3 : κ3-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 [(Me4TACD)SrH(thf)x]+. Complex 3 a decomposed in THF at room temperature to give the terminal silanide complex [(Me4TACD)Sr(SiH3)(thf)2][A], with release of H2. Upon reaction with a weak Brønsted 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 [(Me4TACD)3Sr3(μ2-H)3(μ3-SiH3)2][A], while nOctSiH3 led to the trinuclear (n-octyl)pentahydridosilicate complex [(Me4TACD)3Sr3(μ2-H)3(μ3-SiH5nOct)][A].

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APA

Höllerhage, T., Ghana, P., Spaniol, T. P., Carpentier, A., Maron, L., Englert, U., & Okuda, J. (2022). Formation and Reactivity of a Hexahydridosilicate [SiH6]2− Coordinated by a Macrocycle-Supported Strontium Cation. Angewandte Chemie - International Edition, 61(10). https://doi.org/10.1002/anie.202115379

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