Hard-soft acid-base interactions of silylenes and germylenes

Julianna Oláh, Frank De Proft, Tamás Veszprémi, Paul Geerlings

Research output: Contribution to journalArticle

58 Citations (Scopus)

Abstract

A detailed investigation of the electrophilic and nucleophilic character of singlet silylenes and germylenes, divalent compounds of silicon and germanium, respectively, substituted by first- and second-row elements is presented. In a first part, the Lewis acid properties of these compounds were studied through their complexation reaction with the Lewis bases NH3, PH3, and AsH3. The results indicate that this complexation is most favorable with the hardest base NH3, classifying these compounds as hard Lewis acids. This is confirmed by the linear correlation between the interaction energies and the value of the electrostatic potential, used as an approximation to the local hardness, near the empty p orbital of these compounds, indicating a charge-controlled interaction in the complex. Also the electrophilicity index, proposed by Parr et al., computed both at the global and the local level, correlates linearly with the complexation energies of the compounds with NH3. The Lewis base character of these silylenes has been investigated, through their interaction with the acids BH3 and AlH3. Also in this case, the electrostatic potential can be used to probe the reactivity of the compounds. It will finally be demonstrated that an increasing stability of the silylenes and germylenes is accompanied by an increase in their nucleophilicity and a decrease of the electrophilicity.

Original languageEnglish
Pages (from-to)1608-1615
Number of pages8
JournalJournal of Physical Chemistry A
Volume109
Issue number8
DOIs
Publication statusPublished - Mar 3 2005

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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