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

Six-membered cyclic germoxanes (R 2 GeO) 3 were selectively prepared via the thermal reaction of (alkyl) 2 GeH 2 in dimethylformamide (DMF). Linear metallagermoxanes with an E–O–Ge–O–E backbone (E = Si, Ge, Sn) were prepared by the reaction of Ph 2 GeH 2 with R 3 EH in DMF. Their cyclic and linear germoxane formations were achieved using an iron catalyst, (η (5) -C 5 H 5 )Fe(CO) 2 Me. An iron carbene complex was proposed to be an intermediate in the catalytic reaction.