Ring-Opening Reactions of Tetrahydrofuran versus Alkyne Complexation by Group 4 Metallocene Complexes Leading to General Consequences for Synthesis and Reactions of Metallocene Complexes

The reduction of certain group 4 metallocene dichlorides by magnesium or lithium in the presence or
absence of Me3SiC2SiMe3 in THF or toluene was investigated, giving in the case of titanium the dinuclear
Ti(III) complex [rac-(ebthi)Ti(μ-Cl)]2 (1). For zirconium the 1-oxa-2-zirconacyclohexane 2 was formed
by ring-opening reaction of rac-(ebthi)Zr(η2-Me3SiC2SiMe3) with THF. As a byproduct from the synthesis
of Cp*2Zr(η2-Me3SiC2SiMe3) starting from Cp*2ZrCl2 another 1-oxa-2-zirconacyclohexane (3) was
obtained by ring-opening reaction of THF via the dinuclear complex Cp*2Zr(Cl)-(CH2)4O−Zr(Cl)Cp*2
(4). In the case of hafnium the analogous dinuclear complex Cp*2Hf(Cl)−(CH2)4O−Hf(Cl)Cp*2 (5) and
1-oxa-2-hafnacyclohexane (6) were the main products of the reaction, inhibiting the synthesis of Cp*2Hf(η2-Me3SiC2SiMe3) (7). The tendency for ring opening of THF initiated by metallocenes increases in
the series Ti, Zr, Hf, thus leading to consequences for the synthesis of metallocene complexes.