Aziridinolysis patterns of (NPCl2)3 and (NPCl2)4; crystal structures of trans-N3P3(NC2H4)2Cl4 and 2,trans-4-N4P4(NC2H4)2Cl6

Abstract

The secondary amine aziridine (HNC₂H₄) shows a peculiar competition between geminal and nongeminal substitution in its reactions with both (NPCl₂)₃ and (NPCl₂)₄. This is demonstrated by the formation of the complete series of (isomeric) derivatives N₃P₃(NC₂H₄)_nCl_{6 –n}(n= 1–6) and N₄P₄(NC₂H₄)_nCl_{8 – n}(n= 1–3). Structures are assigned based on ³¹P and ¹H n.m.r. data supported by the crystal-structure determinations of two key compounds, trans-N₃P₃(NC₂H₄)₂Cl₄ and 2,trans-4-N₄P₄(NC₂H₄)₂Cl₆.