Selective replacement of organosilicon units in the cluster [(PhSi)4S6] with coinage metal complex fragments

Abstract

Adamantane-type organo-group 14 chalcogenide clusters were shown to possess extreme non-linear optical properties. Reactivity studies of corresponding organosilicon sulfide clusters towards copper and silver complexes indicate a replacement of exactly one of the organosilicon groups with a metal complex fragment to form [(Et₃PAg)₃(PhSi)₃S₆] (1) and [Na₂(thf)_2.33][(Me₃PCu)(PhSi)₃S₆] (2)—in striking contrast to reactions of organotin chalcogenide clusters, which are more significantly and less systematically re-organized. The silicon compounds are thus more suited for controlled modifications of their geometric and electronic structures.