The ozonation of silanes and germanes: an experimental and theoretical investigation

Janez Cerkovnik, Tell Tuttle, Elfi Kraka, Nika Lendero, Božo Plesničar, Dieter Cremer

Research output: Contribution to journalArticle

39 Citations (Scopus)

Abstract

Ozonation of various silanes and germanes produced the corresponding hydrotrioxides, R3-SiOOOH and R3GeOOOH, which were characterized by 1H, 13C, 17O, and 29Si NMR, and by infrared spectroscopy in a two-pronged approach based on measured and calculated data. Ozone reacts with the E-H (E = Si, Ge) bond via a concerted 1,3-dipolar insertion mechanism, where, depending on the substituents and the environment (e.g., acetone-d6 solution), the H atom transfer precedes more and more E-O bond formation. The hydrotrioxides decompose in various solvents into the corresponding silanols/germanols, disiloxanes/digermoxanes, singlet oxygen (O2(1Δ g)), and dihydrogen trioxide (HOOOH), where catalytic amounts of water play an important role as is indicated by quantum chemical calculations. The formation of HOOOH as a decomposition product of organometallic hydrotrioxides in acetone-d6 represents a new and convenient method for the preparation of this simple, biochemically important polyoxide. By solvent variation, singlet oxygen (O2(1Δ g)) can be generated in high yield.

LanguageEnglish
Pages4090-4100
Number of pages11
JournalJournal of the American Chemical Society
Volume128
Issue number12
Early online date2 Mar 2006
DOIs
Publication statusPublished - 29 Mar 2006

Fingerprint

Silanes
Singlet Oxygen
Ozonization
Acetone
Oxygen
Ozone
Organometallics
Infrared spectroscopy
Magnetic Resonance Spectroscopy
Nuclear magnetic resonance
Decomposition
Atoms
Water
dihydrogen trioxide
silanol
disiloxane

Keywords

  • ozonation
  • infrared spectometry
  • decomposition

Cite this

Cerkovnik, Janez ; Tuttle, Tell ; Kraka, Elfi ; Lendero, Nika ; Plesničar, Božo ; Cremer, Dieter. / The ozonation of silanes and germanes : an experimental and theoretical investigation. In: Journal of the American Chemical Society . 2006 ; Vol. 128, No. 12. pp. 4090-4100.
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The ozonation of silanes and germanes : an experimental and theoretical investigation. / Cerkovnik, Janez; Tuttle, Tell; Kraka, Elfi; Lendero, Nika; Plesničar, Božo; Cremer, Dieter.

In: Journal of the American Chemical Society , Vol. 128, No. 12, 29.03.2006, p. 4090-4100.

Research output: Contribution to journalArticle

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