Abstract Trifluoromethanesulfonates of silicon, germanium, tin and lead are obtained by cleavage of the corresponding phenyl derivatives with CF 3 SO 3 H. Selective cleavage of the tin carbon bond is observed in the case of silyl-and germylstannanes. Reaction of bis ( trifluoromethanesulfonates) with lithiumorganic compounds leads to functional substituted triflate derivatives.