Formation and Reactivity of a Hexahydridosilicate [SiH(6) ](2-) Coordinated by a Macrocycle-Supported Strontium Cation

六氢硅酸盐[SiH(6) ](2-)的形成及其反应活性,该六氢硅酸盐由大环负载的锶阳离子配位。

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Abstract

The cationic benzyl complex [(Me(4) TACD)Sr(CH(2) Ph)][A] (Me(4) TACD=1,4,7,10-tetramethyltetraazacyclododecane; A=B(C(6) H(3) -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) (μ-κ(3)  : κ(3) -SiH(6) )][A](2) (3 a). Rapid phenyl exchange between phenylsilane molecules is assumed to generate monosilane SiH(4) 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(SiH(3) )(thf)(2) ][A], with release of H(2) . Upon reaction with a weak Brønsted acid, CO(2) , and 1,3,5,7-cyclooctatetraene SiH(4) 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) (μ(2) -H)(3) (μ(3) -SiH(3) )(2) ][A], while (n) OctSiH(3) led to the trinuclear (n-octyl)pentahydridosilicate complex [(Me(4) TACD)(3) Sr(3) (μ(2) -H)(3) (μ(3) -SiH(5) (n) Oct)][A].

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