Treatment of the η9,η5-bis(indenyl)zirconium sandwich complex, (η9-C9H5-1,3-(SiMe 3)2)(η5-C9H5-1,3- (SiMe3)2)Zr, with dialkyl ethers such as diethyl ether, CH3OR (R = Et, nBu, tBu), nBu 2O, or iPr2O resulted in facile C-O bond scission furnishing an η5,η5-bis(indenyl)zirconium alkoxy hydride complex and free olefin. In cases where ethylene is formed, trapping by the zirconocene sandwich yields a rare example of a crystallographically characterized, base-free η5, η5-bis(indenyl)zirconium ethylene complex. Observation of normal, primary kinetic isotope effects in combination with rate studies and the stability of various model compounds support a mechanism involving rate-determining C-H activation to yield an η5,η5- bis(indenyl)-zirconium alkyl hydride intermediate followed by rapid β-alkoxide elimination. For isolable η6,η5- bis(indenyl)-zirconium THF compounds, thermolysis at 85 °C also resulted in C-O bond cleavage to yield the corresponding zirconacycle. Both mechanistic and computational studies again support a pathway involving haptotropic rearrangement to η5,η5-bis(indenyl)zirconium intermediates that promote rate-determining C-H activation and ultimately C-O bond scission.
|Original language||English (US)|
|Number of pages||13|
|Journal||Journal of the American Chemical Society|
|State||Published - Dec 27 2006|
All Science Journal Classification (ASJC) codes
- Colloid and Surface Chemistry