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

40 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.

Original languageEnglish
Pages (from-to)4090-4100
Number of pages11
JournalJournal of the American Chemical Society
Volume128
Issue number12
Early online date2 Mar 2006
DOIs
Publication statusPublished - 29 Mar 2006

Keywords

  • ozonation
  • infrared spectometry
  • decomposition

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