N-heterocyclic carbene (NHC)-stabilized silanechalcogenones: NHC-->Si(R2)=E (E=O, S, Se, Te).

A series of N-heterocyclic carbene-stabilized silanechalcogenones 2 a,b (Si=O), 3 a,b (Si=S), 4 a,b (Si=Se), and 5 a,b (Si=Te) are described. The silanone complexes 2 a,b were prepared by facile oxygenation of the carbene-silylene adducts 1 a,b with N(2)O, whereas their heavier congeners were synthesized by gentle chalcogenation of 1 a,b with equimolar amounts of elemental sulfur, selenium, and tellurium, respectively. These novel compounds have been isolated in a crystalline form in high yields and have been fully characterized by a variety of techniques including IR spectroscopy, ESIMS, and multinuclear NMR spectroscopy. The structures of 2 b, 3 a, 4 a, 4 b, and 5 b have been confirmed by single-crystal X-ray crystallography. Due to the NHC-->Si donor-acceptor electronic interaction, the Si=E (E=O, S, Se, Te) moieties within these compounds are well stabilized and thus the compounds possess several ylide-like resonance structures. Nevertheless, these species also exhibit considerable Si=E double-bond character, presumably through a nonclassical Si=E pi-bonding interaction between the chalcogen lone-pair electrons and two antibonding Si-N sigma* orbitals, as evidenced by their high stretching vibration modes and the shortening of the Si-E distances (between 5.4 and 6.3%) compared with the corresponding Si-E single-bond lengths.