This paper deals with the breakdown of polymeric organo-copper(I) and -silver(I) compounds of general type [M I R] n (M = Cu, Ag; R = singly bonded organic or inorganic ligand) to aggregates with lower polynuclearity and to mononuclear M I X species. For the breakdown of the polynuclear structures of organo-copper(I) and -silver(I) compounds, main-group element substituted and organometallic substituted alkynes, diynes, and triynes are used. The synthesis, reactivity and structural features of [M I R] x (x = 1-4) compounds are discussed.