Elemento-Organic Amines and Imines

Amines with mixed substituents containing two or three El? N bonds

1 El = a higher IVa, Va, or VIa element; by IVa, Va, and VIa elements are meant elements of the IV, V, and VI main groups of the periodic system

. 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.