A Stable Schrock-Type Hafnium−Silylene Complex

Abstract

The first stable hafnium-silylene complex, (eta-C5H4Et)2(PMe3)Hf=Si(SiMetBu2)2 (6) was obtained in the form of the phosphine adduct as red crystals by the coupling reaction of 1,1-dilithiosilane (1) with 0.9 equiv of (eta-C5H4Et)2HfCl2 in dry toluene at -50 degrees C, followed by treatment with an excess of PMe3 at -50 degrees C. In the 29Si NMR spectrum of 6, the signal from the silylene ligand is shifted greatly downfield at 295.4 ppm, with a JSiP coupling constant of 15.0 Hz. X-ray crystallographic analysis of 6 revealed that the Si-Hf bond length (2.6515(9) A) is about 5% shorter than typical Si-Hf single bonds, obviously indicating the double-bond character between the silicon and hafnium atoms. The compound 6 was found to be a Schrock-type silylene complex, a conclusion that was supported by the natural population analysis (NPA) charge distribution for the model complex, (eta-C5H4Et)2(PMe3)Hf=Si(SiMe3)2 (8), showing a negative charge on the silicon atom (-0.34).