Theoretical Study of Heavier Group 14 Analogues of Allene

We report the first systematic computational study, using both ab initio and DFT methods, of the heavier group 14 analogues of allene:  R2MCCH2 and H2CMCH2, M = Si, Ge, Sn and Pb, where the substituents R are H, Me, SiH3, and F. The following trends were observed (mostly at B3LYP/SDD):  (a) 1-me...

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Bibliographic Details
Published in:Organometallics 2002-12, Vol.21 (25), p.5486-5493
Main Authors: Sigal, Nadejda, Apeloig, Yitzhak
Format: Article
Language:English
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Summary:We report the first systematic computational study, using both ab initio and DFT methods, of the heavier group 14 analogues of allene:  R2MCCH2 and H2CMCH2, M = Si, Ge, Sn and Pb, where the substituents R are H, Me, SiH3, and F. The following trends were observed (mostly at B3LYP/SDD):  (a) 1-metalaallenes are more stable than 2-metalaallenes for all M elements; (b) in both 1- and 2-metalaallenes the deviation of the skeleton from linearity, the degree of pyramidalization at M, and the planarization energies at M decrease along the series Pb > Sn > Ge > Si; the silaallenes, except for F2SiCCH2, are linear and planar at silicon; (c) the SiH3 substituent favors planarization at M, while F substitution causes strong pyramidalization.
ISSN:0276-7333
1520-6041
DOI:10.1021/om020304p