Electronic structure of stable benzodiazasilylenes: Photoelectron spectra and quantum-chemical investigations

Philip Blakeman, Barbara Gehrhus, Jennifer C. Green, Joachim Heinicke, Michael F. Lappert, Markus Kindermann, T. Veszprémi

Research output: Contribution to journalArticle

30 Citations (Scopus)

Abstract

Photoelectron spectra of 2,3-dihydro-1,3-di(neopentyl)-1H-1,3,2-benzodiazasilol-2-ylidene were investigated and compared to those of 2,3-dihydro-1,3-di(tert-butyl)-1H-1,3,2-diazasilol-2-ylidene and the related 2,3-dihydro-1,3-di(neopentyl)-1H-1,3,2-benzodiazasilole. The experimental spectra were assigned with the help of quantum-chemical calculations using the MP2/6-31G* level of theory. Trends in the orbital energies correspond well with the observed ionization energies. A 0.41 eV stabilization of the highest occupied molecular orbital level from the silane to the related silylene derivative indicates the incorporation of the silicon empty out-of-plane orbital into the π system. A good agreement was found between the calculated and experimental geometries. Delocalization stabilization of the investigated molecules is also supported by appropriate isodesmic reactions. The reaction energy indicates significant aromatic stabilization of the silylene derivatives. The stabilization is, however, reduced by a considerable ring strain.

Original languageEnglish
Pages (from-to)1475-1480
Number of pages6
JournalJournal of the Chemical Society, Dalton Transactions
Issue number8
Publication statusPublished - 1996

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Photoelectrons
Electronic structure
Stabilization
Derivatives
Silanes
Ionization potential
Molecular orbitals
Silicon
Molecules
Geometry

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Electronic structure of stable benzodiazasilylenes : Photoelectron spectra and quantum-chemical investigations. / Blakeman, Philip; Gehrhus, Barbara; Green, Jennifer C.; Heinicke, Joachim; Lappert, Michael F.; Kindermann, Markus; Veszprémi, T.

In: Journal of the Chemical Society, Dalton Transactions, No. 8, 1996, p. 1475-1480.

Research output: Contribution to journalArticle

Blakeman, Philip ; Gehrhus, Barbara ; Green, Jennifer C. ; Heinicke, Joachim ; Lappert, Michael F. ; Kindermann, Markus ; Veszprémi, T. / Electronic structure of stable benzodiazasilylenes : Photoelectron spectra and quantum-chemical investigations. In: Journal of the Chemical Society, Dalton Transactions. 1996 ; No. 8. pp. 1475-1480.
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AU - Lappert, Michael F.

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AU - Veszprémi, T.

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