Hindered cyclopentadienyl rotation in hexakis(trimethylsilyl)metallocene dichlorides of zirconium and hafnium. Evidence for complete rotation of the tris(trimethylsilyl)cyclopentadienyl ligands

Add time:08/01/2019    Source:sciencedirect.com

Reaction of tris(trimethylsilyl)cyclopentadienyllithium with zirconium and hafnium tetrachloride affords 1,1′,2,2′,4,4′-hexakis(trimethylsilyl)zirconocene dichloride and 1,1′,2,2′,4,4′-hexakis(trimethyl-silyl)hafnocene dichloride. These complexes show hindered rotation of the cyclopentadienyl ligands, with barriers to rotation of 11.0±0.02 kcal/mol and 11.3±0.2 kcal/mol being found for the zirconium and hafnium complex, respectively. These values are compared with those of the corresponding 1,1′,3,3′-tetrakis(trimethylsiyl)metallocene dichlorides and a model is proposed to account for the large differences in rotational barriers.

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