TY - JOUR
T1 - Unusual bonding in trisilaallene and related heavy allenes
AU - Kira, Mitsuo
AU - Iwamoto, Takeaki
AU - Ishida, Shintaro
AU - Masuda, Hidenori
AU - Abe, Takashi
AU - Kabuto, Chizuko
PY - 2009/12/2
Y1 - 2009/12/2
N2 - The synthesis, X-ray and spectroscopic analysis, and unusual bonding and structure among heavy group-14 element congeners of allene (heavy allenes) [R2M=M′=MR2; 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 π-σ* mixing (π-σ* 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.
AB - The synthesis, X-ray and spectroscopic analysis, and unusual bonding and structure among heavy group-14 element congeners of allene (heavy allenes) [R2M=M′=MR2; 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 π-σ* mixing (π-σ* 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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U2 - 10.1021/ja904525a
DO - 10.1021/ja904525a
M3 - Article
AN - SCOPUS:72249103225
SN - 0002-7863
VL - 131
SP - 17135
EP - 17144
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 47
ER -