Scrambling of fluoro-, methoxyl, dimethylamino-, and methyl groups with chlorine atoms and of methoxyl with dimethylamino-groups on germanium

Abstract

Equilibrium with respect to exchange of substituents on germanium has been studied by hydrogen nuclear magnetic resonance (n.m.r.) in the systems (1) Ge(OMe)4 with GeCl4, (2) Ge(NMe2)4 with GeCl4, (3) Ge(OMe)4 with Ge(NMe2)4, and (4) GeMe4 with GelCl4. Fluorine n.m.r. was used to study the system (5) GeF4 with GeCl4. The largest deviations from statistically random interchange of the substituents were observed in system (2), with the mixed species being extremely stable. Similar non-random behaviour, with the mixed species being preferred, was found in systems (1) and (4). Exchange of chlorine for fluorine on germanium [system (5)] showed only a small deviation from randomness. The rates of exchange varied greatly, going from a reaction period of many days at 300° for system (4) and many hours at 87° for system (5) to fractions of one second at 25° for systems (1) and (2).