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Updated: Oct 11, 2025
Imine Metathesis by Silica-Supported Catalysts Using the Methodology of Surface Organometallic Chemistry
Published on: October 18, 2019
Formation and Reactivity of a Hexahydridosilicate [SiH6 ]2- Coordinated by a Macrocycle-Supported Strontium Cation
Thomas Höllerhage1, Priyabrata Ghana1, Thomas P Spaniol1
1Institute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1, 52056, Aachen, Germany.
Abstract:
The cationic benzyl complex [(Me4 TACD)Sr(CH2 Ph)][A] (Me4 TACD=1,4,7,10-tetramethyltetraazacyclododecane; A=B(C6 H3 -3,5-Me2 )4 ) reacted with two equivalents of phenylsilane to give the bridging hexahydridosilicate complex [(Me4 TACD)2 Sr2 (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 [(Me4 TACD)SrH(thf)x ]+ . Complex 3 a decomposed in THF at room temperature to give the terminal silanide complex [(Me4 TACD)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 [(Me4 TACD)3 Sr3 (μ2 -H)3 (μ3 -SiH3 )2 ][A], while n OctSiH3 led to the trinuclear (n-octyl)pentahydridosilicate complex [(Me4 TACD)3 Sr3 (μ2 -H)3 (μ3 -SiH5 n Oct)][A].
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