Tetraphosphinitoresorcinarene Complexes: Dynamic Clusters with Silver(I) and Copper(I) Halides

Silver(I) and copper(I) halide derivatives of several tetrakis(diphenylphosphinito)resorcinarene ligands are reported. The complexes [resorcinarene(O2CR)4(OPPh2)4(M5X5)], with resorcinarene = (PhCH2CH2CHC6H2)4, R = C6H11, 4-C6H4Me, C4H3S, OCH2CCH, or OCH2Ph, M = Ag, X = Cl, Br, or I, M = Cu, and X = Cl or I, contain a crownlike [P4M5X5] metal halide cluster. These crown clusters were found to be dynamic in solution, as studied by variable-temperature NMR, and easily fragment to give the corresponding complexes containing [P4M4X5]- and [P4M2((mu)-X)]+ units. Reaction of pentasilver crown clusters with triflic acid gave the corresponding disilver complexes [resorcinarene(O2CR)4(OPPh2)4{Ag2((mu)-Cl)}]CF3SO3. Thus, these resorcinarene-based ligands act as a platform for the easy and reversible assembly of copper(I) and silver(I) clusters with novel structures.