Physical Chemistry

Russian Chemical Bulletin

, Volume 42, Issue 4, pp 663-671

Studies of vacuum pyrolysis of 3-sila- and 3-germa-3,3′-spirobi(6-oxabicyclo[3.1.0]hexanes) and low-temperature matrix stabilization of monomeric silicon dioxide from the gas phase

  • S. E. BoganovAffiliated withN. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences
  • , V. I. FaustovAffiliated withN. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences
  • , V. N. KhabasheskuAffiliated withN. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences
  • , Z. A. KerzinaAffiliated withN. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences
  • , N. D. KagramanovAffiliated withN. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences
  • , A. A. KutinAffiliated withN. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences
  • , O. M. NefedovAffiliated withN. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences
  • , P. MazerollesAffiliated withLaboratory of Organometallic Chemistry, Paul-Sabatier University
  • , G. ManuelAffiliated withLaboratory of Organometallic Chemistry, Paul-Sabatier University

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Abstract

Vacuum pyrolysis of 3-sila-3,3′-spirobi(6-oxabicyclo[3.1.0]hexanes) leads to the formation of monomeric silicon dioxide and 1,3-butadienes, whereas under the same conditions 3-germa-3,3′-spirobi(6-oxabicyclo[3.1.0]hexanes) afford germanium monoxide, the corresponding divinyl ethers, and 1,3-butadienes. A multistage mechanism of pyrolytic decomposition of the above spirobicyclohexanes was proposed on the basis of experimental data and calculations. The different behavior of the silicon and germanium compounds having similar structures can be explained by an increase in the bivalent state stability and by a decrease in the energy of the metal-oxygen double bond on the transition from silicon to germanium.

Key words

vacuum pyrolysis matrix IR spectroscopy semiempirical method AM1 1,1′-dimethyl-3,3′-spirobi(3-germa-6-oxabicyclo[3.1.0]hexane) 1,5-dimethyl-3,3′-spirobi(3-germa-6-oxabicyclo[3.1.0]hexane) 1,5-dimethyl-3,3′-spirobi(6-oxa-3-silabicyclo[3.1.0]hexane) silicon dioxide germanium dioxide germanium monoxide isopropenyl vinyl ether divinyl ether 1,3-butadiene 2,3-dimethyl-1,3-butadiene germanone silanone