Reaction of Pentafulvene Titanium and Zirconium Complexes with Phosphorus Ylides: Stoichiometric Reactions and Catalytic Intramolecular Proton Shuttles
reaction of penta- and benzofulvene complexes of group 4 (M = Ti, Zr) with different phosphorus ylides is reported. Employing the bis(η5:η1-pentafulvene)titanium complexes Ti1a and Ti1b, the reactions with the corresponding phosphorus ylides Y1–5 result in a spontaneous single C–H bond activation and metallocene ylide complexes Ti2a–e can be isolated in good yields. On the basis of these results, this reactivity
2; Ta 4) were investigated. The hexa-coordinate ylide adducts complexes 5 (CpNbCl4(H2CP(NEt2)3)), 6 (Cp∗NbCl4(H2CP(NEt2)3)) and 8 (Cp∗TaCl4(H2CP(NEt2)3)) with pseudo-octahedral geometry were structurally analyzed with X-ray diffraction. Compound 4 (Cp∗TaCl4) reacted with three molar equivalent of phosphorus ylide to form one ionic complex 9 ([H3C-P(NEt2)3][Cp∗TaCl5]) which was also structurally analyzed