Synthesis of bis(indenyl)zirconium dihydrides and subsequent rearrangement to eta5,eta3-4,5-dihydroindenediyl ligands: evidence for intermediates during the hydrogenation to tetrahydroindenyl derivatives.

Exposure of eta9,eta5-bis(indenyl)zirconium sandwich complexes to 4 atm of H2 resulted in facile oxidative addition to furnish the corresponding zirconocene dihydrides, (eta5-C9H5-1,3-R2)2ZrH2 (R = SiMe3, SiMe2Ph, CHMe2). Continued hydrogenation completed conversion to the tetrahydroindenyl derivatives, (eta5-C9H9-1,3-R2)2ZrH2. Deuterium labeling studies established that dihydrogen (dideuterium) addition to the benzo rings is intramolecular and stereospecific, occurring solely from the endo face of the ligand, proximal to the zirconium. In the absence of dihydrogen, the bis(indenyl)zirconium dihydrides rearranged to new zirconium monohydride complexes containing an unusual eta5,eta3-4,5-dihydroindenediyl ligand, arising from metal-to-benzo ring hydrogen transfer. Mechanistic studies, including a normal, primary kinetic isotope effect measured at 23 degrees C, are consistent with a pathway involving regio- and stereoselective insertion of a benzo C=C bond into a zirconium hydride. The stereochemistry of the insertion reaction, and hence the eta5,eta3-4,5-dihydroindenediyl product, is influenced by the presence of donor ligands and controlled by the preferred conformation of the indenyl rings. Exposure of the zirconium hydrides containing the eta5,eta3-4,5-dihydroindenediyl rings to 1 atm of dihydrogen afforded the tetrahydroindenyl zirconium dihydride complexes, establishing the intermediacy of this unusual coordination environment during benzo ring hydrogenation.