Unusual Bonding in Trisilaallene and Related Heavy Allenes
Journal of the American Chemical Society2009Vol. 131(47), pp. 17135–17144
Citations Over TimeTop 10% of 2009 papers
Abstract
The synthesis, X-ray and spectroscopic analysis, and unusual bonding and structure among heavy group-14 element congeners of allene (heavy allenes) [R(2)M=M'=MR(2); M = M' = Si (1a), M = Si, M' = Ge (1b), M = Ge, M' = Si (1c), and M = M' = Ge (1d)] are comparatively discussed. Using DFT calculations and PMO theory, the origin of the bent and fluxional skeleton of the heavy allenes is ascribed to the Jahn-Teller distortion associated with the effective pi-sigma* mixing (pi-sigma* distortion). This type of distortion is suggested to be a key concept for qualitative description of the unusual bonding of unsaturated compounds of heavy main-group elements.
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