STERICALLY HINDERED GERMANIUM-NITROGEN BOND .2. N-MONOHALOGERMANYL SECONDARY AMINES

Within a general study of new precursors of germa-imines, a series of N-monohalogermyl secondary amines of the type R2Ge(X)NHR' (R= Me, Et, Ph ; R'= Mes, tBu3C6H2 ; X= Cl, F) stabilized by steric hindrance was synthesized. These compounds were obtained through aminolysis of germanium-halogen bonds by primary amines or by lithium derivatives of these primary amines. The halogermylamines thus formed are thermally unstable and decompose by symmetrisation leading principally to the corresponding dihalogermanes. Methanolysis of the Ge-N bond leads to the corresponding halomethoxygermanium compounds. Abstraction of hydrogen halide leads to the expected transient germa-imine or to the corresponding dimer: the sterically hindered cyclodigermazane not obtainable by other methods. Cleavage reactions of sterically hindered cyclodigermazanes by Et3N,HCl does not lead to halogermyl secondary amines but to bis(diorganohalogermyl) tertiary amines.