Functionalised trimethylsilyl reagents in cluster synthesis: reactions of Ph2P(S)SSiMe3 with group 11 salts

A series of complexes, ranging from the small cluster 1/infinity[Ag(Ph2PS2)(dppe)](infinity) [dppe = 1,2-bis(diphenylphosphino)ethane] to [Cu48S20((OBu)-Bu-t)(2)(Ph2PS2)(2)(dppm(-))(4)(dppm)(4)] [dppm = 1,2- bis(diphenylphosphino)methane] (the largest Cu cluster containing phosphinodithioato ligands), has been synthesised. The structural evidence presented here indicates that in these reactions initially small cyclic aggregates or one-dimensional coordination polymers are formed. The growth of these intermediates to larger aggregates can take up to several months and could proceed via cationic intermediates.