Conformational and coordination plasticity in silver(i) cryptates

Abstract

The structure of a disilver aminocryptate with silver accommodated in the faces rather than within the tetramine-derived caps of the crypt shows close contact between Ag⁺ cations indicative of interaction between the d¹⁰ cations. On standing in solution, a second, trisilver, cryptate is isolated, where close contact between the silver cations, now triangularly disposed, is still present. A pseudoreversible wave close to 0 V vs. Ag/AgCl is tentatively assigned to the one-electron I,I ↔ I,O redox process in the disilver cryptate.