Partial hydrolysis of Ti(III) and Ti(IV) chlorides in the presence of [PPh4]Cl

摘要

Partial hydrolysis of Ti(III) and Ti(IV) chlorides in the presence of [PPh4]Cl yielded a series of new complexes. Ti(III) chloride was obtained from reduction of TiCl4 with 1 equiv. of HSnBu3. In CH2Cl2 in the presence of TiCl4, the hydrolysis reaction led to the formation of a Ti(III)-Ti(IV) mixed valent complex, namely, heptanuclear [PPh4](3)[Ti7Cl19O3] (2) containing three face-sharing Ti-2 units and three edge-sharing Ti-2 units. When the reaction was conducted in acetone, only two Ti(III) complexes, namely, dinuclear edge-sharing [PPh4](2)[Ti2Cl7(OH)(H2O)(OCMe2)] (3) and mononuclear [TiCl3(H2O)(3)] (4), were obtained. The hydrolysis products of TiCl4 in the presence of [PPh4]Cl include a one-dimensional polymeric compound, {[PPh4][Ti2Cl6X]O}(n) (X=Cl, OH) (5), and a mononuclear complex, {PPh4][TiCl5(H2O)] (6). The simple addition product, [PPh4](2)[TiCl6] (7), was also isolated from this reaction. Compounds 2-7 were all characterized by X-ray crystallography. (C) 1998 Elsevier Science S.A. [References: 32]