Dianionic species with a bond consisting of two pentacoordinated silicon atoms

Abstract

Silicon can form bonds to other tetracoordinated silicon atoms and these bonds form the framework of many organosilicon compounds and crystalline silicon. Silicon can also form a pentacoordinated anionic structure—a so-called ‘silicate’. No compounds containing a direct bond between two silicate moieties—‘disilicates’ where two silicate structures are combined in one species—have been reported because of the electronic repulsion between the anionic halves and difficulty preventing the release of anions. Here we report the synthesis of thermally stable and isolable disilicates by the reductive coupling reaction of a silane bearing two electron-withdrawing bidentate ligands. Two pentacoordinated silicons, positively charged despite the formal negative charge, constitute a single σ-bond and bind eight negatively charged atoms. They can be reversibly protonated, cleaving two Si–O bonds, to afford a tetracoordinated disilane. Their unique electronic properties could be promising for the construction of functional materials with silicon wire made up of silicate chains. Silicon, like carbon, favours a four-coordinate geometry and this underpins the frameworks of the wide range of inorganic and organosilicon compounds, from silicate minerals to polysilanes. Although some pentavalent silicon compounds have already been reported, this work presents the first example where two five-coordinate silicon atoms are bonded to each other.

Cite this article

Kano, N., Miyake, H., Sasaki, K. et al. Dianionic species with a bond consisting of two pentacoordinated silicon atoms. Nature Chem 2, 112–116 (2010). https://doi.org/10.1038/nchem.513

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