Why are the {Cu4N4} rings in copper(I) phosphinimide clusters [Cu{μ-N=PR3}]4 (R = NMe3 or Ph) planar?

Abstract

The copper phosphinimide complexes [Cu{μ-NPR3}]4 (1, R = NMe2 and 2, R = Ph) were obtained in good yields from the reactions of Cu[Mes] (Mes = mesityl, C6H2Me3-2,4,6) with the corresponding iminophosphoranes, HNPR3. The molecular structures of 1 and 2 reveal the presence of planar eight-membered {Cu4N4} rings which contrasts with the saddle-shaped {M4N4} rings found in related metal phosphinimide complexes. According to computations, there is negligible aromaticity in the planar {Cu4N4} rings in 1 and 2 and the saddle shape observed in related {M4N4} rings is due to steric factors.