ELEMENTO-ORGANIC AMINES AND IMINES

Amines with mixed substituents containing two or three ElN bonds . are relatively stable if one or two of these bonds are (CH3)3 SiN bonds. IR and 1HNMR studies indicate that the (p → d)π bond components of the element‐nitrogen bonds steadily decrease from silicon, phosphorus, and sulfur toward their higher homologs. Because of the differences in the polarities of the element‐nitrogen bonds, these substances can be used for selective insertion and cleavage reactions. The reaction of metalated N‐silylaminoarsines with methyl chloride as well as the reaction of metalated N‐trimethyl(IVa)‐element‐substituted amino‐tert‐butylphosphines with halogenotrimethyl(IVa) element compounds open new, simple routes for the conversion of elemento‐organic amine systems into imine systems. The problem of reversible and irreversible (CH3)3 El ligand migration (1,3 shift) is discussed for trimethyl(IVa)element‐substitued benzamidines, diaminophosphines, aminoiminophosphoranes, sulfinamides, and aminosulfimines. Copyright © 1969 by Verlag Chemie, GmbH, Germany