由大环支撑的锶阳离子配位的六氢硅酸盐[SiH]的形成与反应活性
Formation and Reactivity of a Hexahydridosilicate [SiH ] Coordinated by a Macrocycle-Supported Strontium Cation.
作者信息
Höllerhage Thomas, Ghana Priyabrata, Spaniol Thomas P, Carpentier Ambre, Maron Laurent, Englert Ulli, Okuda Jun
机构信息
Institute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1, 52056, Aachen, Germany.
CNRS, INSA, UPS, UMR 5215, LPCNO, Université de Toulouse, 135 avenue de Rangueil, 31077, Toulouse, France.
出版信息
Angew Chem Int Ed Engl. 2022 Mar 1;61(10):e202115379. doi: 10.1002/anie.202115379. Epub 2022 Jan 14.
The cationic benzyl complex [(Me TACD)Sr(CH Ph)][A] (Me TACD=1,4,7,10-tetramethyltetraazacyclododecane; A=B(C H -3,5-Me ) ) reacted with two equivalents of phenylsilane to give the bridging hexahydridosilicate complex [(Me TACD) Sr (thf) (μ-κ : κ -SiH )][A] (3 a). Rapid phenyl exchange between phenylsilane molecules is assumed to generate monosilane SiH that is trapped by two strontium hydride cations [(Me TACD)SrH(thf) ] . Complex 3 a decomposed in THF at room temperature to give the terminal silanide complex [(Me TACD)Sr(SiH )(thf) ][A], with release of H . Upon reaction with a weak Brønsted acid, CO , and 1,3,5,7-cyclooctatetraene SiH was released. The reaction of a 1 : 2 mixture of cationic benzyl and neutral dibenzyl complex with phenylsilane gave the trinuclear silanide complex [(Me TACD) Sr (μ -H) (μ -SiH ) ][A], while OctSiH led to the trinuclear (n-octyl)pentahydridosilicate complex [(Me TACD) Sr (μ -H) (μ -SiH Oct)][A].
阳离子苄基配合物[(Me TACD)Sr(CH₂Ph)][A]（Me TACD = 1,4,7,10 - 四甲基四氮杂环十二烷；A = B(C₆H₂ - 3,5 - Me₂)₄）与两当量的苯基硅烷反应，生成桥连六氢硅酸盐配合物[(Me TACD)₂Sr₂(thf)(μ - κ²:κ² - SiH₂)][A]（3a）。假定苯基硅烷分子之间快速的苯基交换生成单硅烷SiH₄，其被两个氢化锶阳离子[(Me TACD)SrH(thf)]捕获。配合物3a在室温下于四氢呋喃中分解，生成末端硅化物配合物[(Me TACD)Sr(SiH₃)(thf)][A]，并释放出H₂。与弱酸、CO₂以及1,3,5,7 - 环辛四烯反应时会释放出SiH₄。阳离子苄基和中性二苄基配合物1:2混合物与苯基硅烷反应，生成三核硅化物配合物[(Me TACD)₂Sr₂(μ - H)₂(μ³ - SiH₂)₂][A]，而OctSiH则生成三核（正辛基）五氢硅酸盐配合物[(Me TACD)₂Sr₂(μ - H)₂(μ³ - SiH₂Oct)₂][A]。
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