Synthesis, Molecular Structure, and Racemate−Meso Interconversion for rac-(Me2Si)25-C5H-3-(CHMe2)-5-Me}2MCl2 (M = Ti and Zr)

Autor: Miyake, S., Henling, L. M., Bercaw, J. E.
Zdroj: Organometallics; December 7, 1998, Vol. 17 Issue: 25 p5528-5533, 6p
Abstrakt: Doubly [SiMe2]-bridged group IV metallocenes, rac-(Me2Si)25-C5H-3-(CHMe2)-5-Me}2MCl2 (M = Ti, Zr), have been synthesized, and a crystal structure of rac-(Me2Si)25-C5H-3-(CHMe2)-5-Me}2TiCl2 has been determined by X-ray diffraction methods. Racemate−meso interchange occurs in benzene solution just above room temperature, affording an approximately 1:1 mixture of rac-(Me2Si)25-C5H-3-(CHMe2)-5-Me}2TiCl2 and meso-(Me2Si)25-C5H-3-(CHMe2)-5-Me}2TiCl2. Measurements of the kinetics of the approach to equilibrium reveal ΔH&thermod; = 18(1) kcal·mol-1 and ΔS&thermod; = −7(2) eu. The corresponding zirconium compound is configurationally stable.
Databáze: Supplemental Index