Deactivation of arenetitanium(II) bromoalane complexes in the cyclotrimerization of butadiene

Abstract

The C6H6.Ti(II)(AlBr4)2 (Ib) catalyst deactivates during the butadiene cyclotrimerization to give a solid containing all titanium (mostly as TiBr3) and a mixture of AlBr3 and RAlBr2 compounds dissolved in benzene. The residual cationic catalytic activity of the deactivated Ib system is due to presence of AlBr3. In contrast to TiCl3, the deactivated Ib system and the model system TiBr3 + AlBr3 are not activated by the addition of EtAlCl2 in the presence of butadiene: the highly active benzenetitanium(II) system is re-constituted only after reduction of TiBr3 with Et3Al followed by the addition of EtAlCl2. The addition of Et2AlBr to Ib accelerates the deactivation of the system. Deactivation products of this system contain mainly Ti(II) species which forms benzenetitanium(II) catalytic system after addition of EtAlCl2. All the EtAlCl2 reactivated systems produce (Z, E, E)-1,5,9-cyclododecatriene with high catalytic stability and considerable selectivity (>90%). This behaviour points to the catalysis by benzenetitanium(II) chloroalane complexes containing only low amount of bromine atoms and ethyl groups.