Synthesis of bimetallic cage-like metalloorganosiloxanes from polymeric metallosiloxanes

A new approach to the synthesis of the cage-like metalloorganosiloxanes (MOS) was developed. Unlike existing schemes for the synthesis of the cage-like MOS from monomeric structural units, regular polyhedral structures were formed from irregular polymeric MOS by their reaction with sodium phenylsilanolate. Efficiency of the method suggested was confirmed by directed synthesis of the earlier described bimetallic cage-like (CuII,Na)- and (FeIII,Na)-phenylsiloxanes in 69 and 47% yields, respectively. Compounds that obtained were identified by destructive trimethylsilylation, GPC, 1H NMR, and X-ray crystallography.