The Lewis acidity of bis(catecholato)silanes is scaled and rationalized. Perbromination of the catechols provides the strongest silicon Lewis superacid.
Catechols occupy
a unique role in the structural, bio-, and geochemistry
of silicon. Although a wealth of knowledge exists on their hypercoordinate
complexes, the structure of tetracoordinate bis(catecholato)silane,
Si(catH)2
1, has been enigmatic
since its first report in 1951. Indeed, the claim of a planar-tetracoordinated
silicon in 1 triggered a prominent debate, which is unsettled
to this day. Herewith, we present a comprehensive structural study
on 1 and derivatives in the gas phase by electron diffraction,
in a neon matrix by IR spectroscopy, in solution by diffusion NMR
spectroscopy, and in the solid-state by X-ray diffraction and MAS
NMR spectroscopy, complemented by high-level quantum-chemical computations.
The compound exhibits unprecedented phase adaptation. In the gas phase,
the monomeric bis(catecholato)silane is tetrahedral, but in the condensed
phase, it is metastable toward oligomerization up to a degree controllable
by the type of catechol, temperature, and concentration. For the first
time, spectroscopic evidence is obtained for a rapid Si–O σ-bond
metathesis reaction. Hence, this study sorts out a long-lasting debate
and confirms dynamic covalent features for our Earth’s crust’s
most abundant chemical bond.
The heterolytic cleavage of dihydrogen constitutes the hallmark reaction of frustrated Lewis pairs (FLP). While being well‐established for planar Lewis acids, such as boranes or silylium ions, the observation of the primary H2 splitting products with non‐planar Lewis acid FLPs remained elusive. In the present work, we report bis(perfluoro‐N‐phenyl‐ortho‐amidophenolato)silane and its application in dihydrogen activation to a fully characterized hydridosilicate. The strict design of the Lewis acid, the limited selection of the Lewis base, and the distinct reaction conditions emphasize the narrow tolerance to achieve this fascinating process with a tetrahedral Lewis acid.
High molar weight polyphosphinoboranes represent materials with auspicious properties, but their preparation requires transition metal-based catalysts. Here, calix[4]pyrrolato aluminate is shown to induce the dehydropolymerization of phosphine boranes to high molar mass polyphosphinoboranes (up to M n = 43 000 Da). Combined GPC and 31 P DOSY NMR spectroscopic analyses, quantum chemical computations, and stoichiometric reactions disclose a PÀ H bond activation by the cooperative action of the square-planar aluminate and the electron-rich ligand framework. This first transition metal-free catalyst for PÀ B dehydrocoupling overcomes the problem of residual d-block metal impurities in the resulting polymers that might interfere with the reproducibility of the properties for this emerging class of inorganic materials.
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