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Theoretical Study of Heavier Group 14 Analogues of Nadejda Sigal and Yitzhak Apeloig*

Summary: Theoretical Study of Heavier Group 14 Analogues of
Nadejda Sigal and Yitzhak Apeloig*
Department of Chemistry and the Lise Meitner-Minerva Center for Computational Quantum
Chemistry, Technion-Israel Institute of Technology, Haifa 32 000, Israel
Received April 17, 2002
We report the first systematic computational study, using both ab initio and DFT methods,
of the heavier group 14 analogues of allene: R2MdCdCH2 and H2CdMdCH2, 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 F2SidCdCH2, are linear and
planar at silicon; (c) the SiH3 substituent favors planarization at M, while F substitution
causes strong pyramidalization.
The chemistry of low-coordinated compounds contain-
ing the heavier group 14 elements, Si, Ge, Sn, and Pb,
has attracted much attention in the last two decades
because of their unique structures and reactivity and


Source: Apeloig, Yitzhak - Department of Chemistry, Technion, Israel Institute of Technology


Collections: Chemistry