Molecular tailoring: Reaction path control with bulky substituents

Tibor Szilvási, T. Veszprémi

Research output: Article

25 Citations (Scopus)

Abstract

Steric groups are often regarded in reactions as chemically irrelevant, inert parts of the molecules, which have no influence on the structure of the forming reactive center of the product but rather on the reaction rate; therefore, they are usually not taken into account in theoretical work. However, in some cases, e.g. in the general reaction scheme of reductive dehalogenation of halosilanes, bulky substituents can cause major structural changes in the product simply by their presence. Our calculations using real substituents suggest that the use of proper substituents can prefer and stabilize only one structure on the potential energy surface (PES), eliminating all other relevant minima, not just increasing activation barriers as chemical intuition dictates. Since the preparation of these compounds are generally unpredictably slow process, the theoretical design may bring fundamental breakthroughs in the field of the synthesis of hitherto unknown reactive compounds. With the help of this concept, one can easily design proper substituents for the synthesis of a specific structure, since the mapping of the reaction routes can be spared and only a few calculations are needed. To illustrate the concept in practice, we suggest substituents, asymmetric R-Ind and terpenyl groups, for the synthesis of hexasilabenzene, which is one of the most desired silicon compounds.

Original languageEnglish
Pages (from-to)3207-3212
Number of pages6
JournalOrganometallics
Volume31
Issue number8
DOIs
Publication statusPublished - ápr. 23 2012

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Silicon Compounds
synthesis
Dehalogenation
silicon compounds
Potential energy surfaces
products
Reaction rates
reaction kinetics
Chemical activation
potential energy
routes
activation
preparation
Molecules
causes
molecules

ASJC Scopus subject areas

  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Molecular tailoring : Reaction path control with bulky substituents. / Szilvási, Tibor; Veszprémi, T.

In: Organometallics, Vol. 31, No. 8, 23.04.2012, p. 3207-3212.

Research output: Article

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