Single crystal X-ray studies have defined the structures of a number of adducts of the form MX:dpex (2:1), M=univalent coinage metal (Cu, Ag), X=(pseudo-)halide, dpex=bis(diphenylpnicogeno)alkane, Ph 2 E(CH 2 ) x EPh 2 , E=P, As, of diverse types, some novel. The adducts of AgCl,Br:dppm and AgNCO:dpem (x=1) are tetranuclear as is the AgNO 3 :dppp (x=3) array, all derivative of the familiar ‘step’ structure while the combination CuCN:dppm yields a two-dimensional web of twenty-membered macro/metallacycles. Synthetic procedures for all adducts have been reported. All compounds have been characterized both in solution ( 1 H, 13 C, 31 P NMR, ESI MS) and in the solid state (IR).