Preparation, characterization and reactivity of Cp 2M(PMe 3) 2 complexes (M = Ti, Zr): the molecular structure of Cp 2Zr(PMe 3) 2

Abstract

The reduction of Cp 2MCl 2 (M = Ti, Zr) with magnesium in THF in the presence of PMe 3 affords the complexes Cp 2M(PMe 3) 2 in high yields. These compounds lose one or both PMe 3 ligands under very mild conditions. Cp 2Ti(PMe 3) 2 reacts readily with CH 3I, CH 3C(O)Cl, PhSSPh, Me 2PCH 2CH 2PMe 2, CO, RCN (R = Me, t-Bu) or (RN) 2S (R = t-Bu, Me 3Si) to give the corresponding titanocene products. The structure of Cp 2Zr(PMe 3) 2 has been determined by X-ray diffraction; the structural parameters are similar to those of the titanium analog Cp 2Ti(PMe 3) 2 except that the Zr-P and Zr-C distances are longer.