A Barium Complex of the Silanide SiH 3 - : Hydride Surrogate and Source of Silicon.

The silanide SiH 3 - is an archetypical anion. Its metathesis chemistry is, however, still underdeveloped. We have conveniently prepared the barium silanide complex [( dtbp Cbz)BaSiH 3 ] 8 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 [( dtbp Cbz)Ge] + , transfer of SiH 3 - was observed, and the decomposition of the silylgermylene [( dtbp Cbz)GeSiH 3 ] was studied. For the heavier, more easily reducible congeners [( dtbp Cbz)Sn] + and [( dtbp Cbz)Pb] + as substrates, [( dtbp Cbz)SiH 3 ] was obtained under elimination of elemental Sn and Pb, so that formally SiH 3 + was transferred to the dtbp Cbz - ligand.