Collect. Czech. Chem. Commun. 1981, 46, 3088-3096

A comparative study of the SF6-sensitized interaction of a cw-CO2 laser radiation with methyltrichloro derivatives of carbon, silicon and germanium

Josef Polaa, John M. Bellamab and Václav Chvalovskýa

a Institute of Chemical Process Fundamentals, Czechoslovak Academy of Sciences, 165 02 Prague 6-Suchdol, Czechoslovakia
b Chemistry Department, University of Maryland, College Park, Maryland 207 42, U.S.A.


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.