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).