Institute of Inorganic Chemistry (AOC), Karlsruhe Institute of Technology (KIT), Engesserstr. 15, Gebäude 30.45, 76131 Karlsruhe, Germany.
Inorg Chem. 2023 Jul 3;62(26):10249-10255. doi: 10.1021/acs.inorgchem.3c01045. Epub 2023 Jun 21.
The silanide SiH is an archetypical anion. Its metathesis chemistry is, however, still underdeveloped. We have conveniently prepared the barium silanide complex [(Cbz)BaSiH] with a bulky carbazolide ligand by reaction of the corresponding barium amide with phenyl silane in a good yield. The silanide complex was then used in various metathesis reactions, displaying distinct reactivity toward different substrates. Toward organic substrates such as carbodiimide or benzophenone, the silanide acted as a hydride surrogate, and formamidinate or diphenylmethoxide ligands were formed. Toward the monocoordinated cation [(Cbz)Ge], transfer of SiH was observed, and the decomposition of the silylgermylene [(Cbz)GeSiH] was studied. For the heavier, more easily reducible congeners [(Cbz)Sn] and [(Cbz)Pb] as substrates, [(Cbz)SiH] was obtained under elimination of elemental Sn and Pb, so that formally SiH was transferred to the Cbz ligand.
硅烷化物 SiH 是典型的阴离子。然而，其交叉化学仍然不够发达。我们通过相应的钡酰胺与苯基硅烷在良好产率下反应，方便地制备了具有大体积咔唑化物配体的钡硅烷化物复合物 [(Cbz)BaSiH]。然后，该硅烷化物复合物被用于各种交叉反应，对不同的底物表现出明显的反应性。对于有机底物如碳二亚胺或二苯甲酮，硅烷化物充当氢化物替代物，形成甲脒基或二苯甲氧基配体。对于单配位阳离子 [(Cbz)Ge]，观察到 SiH 的转移，并且研究了甲硅烷基锗 [(Cbz)GeSiH] 的分解。对于较重、更容易还原的同系物 [(Cbz)Sn] 和 [(Cbz)Pb] 作为底物，在消除元素 Sn 和 Pb 的情况下获得了 [(Cbz)SiH]，因此 SiH 形式上被转移到 Cbz 配体上。
