Among four different 2-D polymericsilver(I)–bpfb assemblies synthesized, [Ag(μ-bpfb)(N3)]n (4c) having an azide anion was shown to be the best catalyst for the partial oxidation of primary amines to N-monoalkylhydroxylamines with urea hydrogen peroxide (UHP). The method has supplied the minimum E-Factor (which is in the range for bulk chemicals) amongst all of the presented methods. More importantly