Catalytic Synthesis of Cyclic and Linear Germoxanes Mediated by an Iron Complex

Six-membered cyclic germoxanes (R2GeO)3 were selectively prepared via the thermal reaction of (alkyl)2GeH2 in dimethylformamide (DMF). Linear metallagermoxanes with an E–O–Ge–O–E backbone (E = Si, Ge, Sn) were prepared by the reaction of Ph2GeH2 with R3EH in DMF. Their cyclic and linear germoxane formations were achieved using an iron catalyst, (η-C5H5)­Fe­(CO)2Me. An iron carbene complex was proposed to be an intermediate in the catalytic reaction.