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(O(2)CR)(4)(OPPh(2))(4)(M(5)X(5))], with resorcinarene = (PhCH(2)CH(2)CHC(6)H(2))(4), R = C(6)H(11), 4-C(6)H(4)Me, C(4)H(3)S, OCH(2)CCH, or OCH(2)Ph, M = Ag, X = Cl, Br, or I, M = Cu, and X = Cl or I, contain a crownlike [P(4)M(5)X(5)] 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 [P(4)M(4)X(5)](-) and [P(4)M(2)(micro-X)](+) units. Reaction of pentasilver crown clusters with triflic acid gave the corresponding disilver complexes [resorcinarene(O(2)CR)(4)(OPPh(2))(4)]Ag(2)(micro-Cl)]]CF(3)SO(3). 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.