Collection of Czechoslovak Chemical Communications - digital archive 

Abstract

A comparative study of the gas-phase interaction of methyltrichloro derivatives of carbon, silicon and germanium (CH₃MCl₃ where M = C, Si and Ge) with sulfur hexafluoride either excited by a cw-CO₂ laser radiation or under conventional static pyrolytic conditions is reported. 1,1,1-Trichloroethane and methyltrichlorogermane do not react with SF₆ under laser irradiation and undergo their decomposition leading to the same products as afforded by heating: CH₃CCl₃ yields Cl₂C=CH₂ and HCl, and CH₃GeCl₃ gives HGeCl₃ along with CH₄ and C₂H₂. Mixtures of methyltrichlorosilane and SF₆ afford under the both conditions products of the CH₃SiCl₃ decomposition -CH₄, C₂H₂, HCl and SiCl₄ and products of the CH₃SiCl₃-SF₆ reaction -SiF₄, SCF₂ and CS₂. Possible reasons for the different reactivity of CH₃MCl₃ compounds toward SF₆ are briefly discussed. The decompositions of CH₃GeCl₃ to HGeCl₃ offers new way for the preparation of the latter compound.