Page 148 - Arrow Pushing in Inorganic Chemistry A Logical Approach to the Chemistry of the Main Group Elements

GROUP 14 ELEMENTS
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6. Presumably because of the longer bonds to silicon, silyl cations are much more reac-
tive than analogous carbocations. They are extraordinarily powerful Lewis acids and
have recently been applied as such to novel synthetic problems. One such application
that we have discussed is fluoride ion abstraction.

FURTHER READING
For most topics, we recommend the textbooks listed in Appendices 1 and 2. The following focus
on more specialized topics, especially low coordination-number compounds, which have yet to be
discussed in current inorganic texts:

1. For reviews on the -silicon effect, see (a) Lambert, J. B. “The Interaction of Silicon with Posi-
tively Charged Carbon” Tetrahedron 1990, 46, 2677–2689. (b) Lambert, J. B.; Zhao, Y.; Emblidge,
R. W.; Salvador, L. A.; Liu, X.; So, J. H.; Chelius, E. C. “The Effect of Silicon and Related
Manifestations of Conjugation” Acc. Chem. Res. 1999, 32, 183–190. And references contained
therein.
2. Mizuhata, Y.; Sasamori, T.; Tokitoh, N. “Stable Heavier Carbene Analogues,” Chem. Rev. 2009,
109, 3479–3511. A comprehensive survey of the field.
3. Power, P. “Interaction of Multiple Bonded and Unsaturated Heavier Main Group Compounds with
Hydrogen, Ammonia, Olefins, and Related Molecules,” Acc. Chem. Res. 2011, 44, 627–637.
+
4. Reed, C. A. “The Silylium Ion Problem, R Si . Bridging Organic and Inorganic Chemistry,” Acc.
3
Chem. Res. 1998, 31, 325–332. A review by a major contributor to the field.
5. Klare, H. F. T.; Oestreich, M. “Silylium Ions in Catalysis,” Dalton Trans. 2010, 39, 9176–9184.
A short and excellent introduction to a topic of current interest.