Reactions of M[(η5-C5Me5)Fe(CO)2] with ClSiMe2NR2 in THF, Et2O and toluene (M = Li and K; R = Me, Et, iPr and Ph)

Abstract

Treatment of K[Cp*Fe(CO)₂] (Cp* = η⁵-C₅Me₅) with ClSiMe₂NR₂ (R = Me, Et, ⁱPr, Ph) in THF afforded Cp*(CO)₂Fe(CH₂)₄OSiMe₂NR₂ accompanied with ring-opening and incorporation of a THF molecule between iron and silicon atoms. On the other hand, reactions between Li[Cp*Fe(CO)₂] and ClSiMe₂NR₂ in diethyl ether (for R = Me, Et), or in toluene in the presence of N,N,N′,N′-tetramethylethylenediamine (TMEDA) (for R = ⁱPr, Ph) afforded the corresponding Cp*(CO)₂FeSiMe₂NR₂ (R = Me, Et, ⁱPr, Ph), where the anionic complex was freshly prepared by treatment of Cp*(CO)₂FeH with n-BuLi. In the case of the reaction of Li[Cp*Fe(CO)₂] with ClSiMe₂NPh₂, although the formation of the diphenylamino derivative Cp*(CO)₂FeSiMe₂NPh₂ was confirmed by NMR spectroscopy, purification of the product was unsuccessful. Subsequently, the exclusive formation of Cp*(CO)₂FeSiMe₂NPh₂ was achieved by means of irradiation of Cp*(CO)₂FeMe and HSiMe₂NPh₂ in toluene.