An unusual germole-to-silole transformation is described. As key intermediates hetero-fulvenes are formed which rearrange to more stable bicyclic carbene analogues. The so-formed germylenes undergo a reductive elimination yielding elemental germanium and siloles. In contrast, the analogous silylenes are stable at ambient conditions and were identified by MS spectrometry and NMR spectroscopy supported by the results of quantum mechanical calculations. These bicyclic silylenes are stable derivatives of the global minimum of the C Si H potential energy surface.
Treatment of potassium salts of silole dianions with donor stabilised germanium dichlorides gave the anticipated silagermafulvenylidenes R2Si=Ge(Do) (R2Si = 1-silacyclopentadiendiyl, Do = N-heterocyclic carbene (NHC)) only as transient intermediates in...
An unprecedented germole to silole transformation opened the way for the synthesis of novel silylenes based on a bicyclohexene skeleton, so‐called BCH silylenes. The astonishing stability of BCH silylenes results from homoconjugation between the dicoordinated Si atom and a remote C=C bond. This stabilization is more efficient than conventional electron delocalization, indicated by the fact that BCH silylenes are stable derivatives of the global minimum of the C4Si2H6 potential energy surface. More information can be found in the Full Paper by T. Müller et al. on page 848.
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