Details

Autor(en) / Beteiligte

• Klosin, Jerzy
• Kruper, William J.
• Patton, Jasson T.
• Abboud, Khalil A.

Titel

Synthesis and X-ray structure of novel 2- and 3-heteroatom-substituted ansa-zirconocene complexes

Ist Teil von

• Journal of organometallic chemistry, 2009-07, Vol.694 (16), p.2581-2596

Ort / Verlag

Elsevier B.V

Erscheinungsjahr

2009

Link zum Volltext

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• New ansa-zirconocene complexes with amino and alkoxy substituents attached to the η 5-bonded indenyl fragment have been synthesized. Crystallographic analysis showed that heteroatom substituents, especially those in the 3-position on the indenyl ligand, have a substantial effect on the structure of metallocenes leading to an increase in the gap aperture in those complexes. New ansa-zirconocene complexes with amino ( 8– 11) and alkoxy ( 12) substituents attached to the η 5-bonded indenyl fragment have been synthesized by the reaction of ZrCl 4 with the appropriate dilithium salt in toluene. In addition to HRMS, NMR spectroscopy, and elemental analysis, all new metallocenes have been characterized by single crystal X-ray analysis. Crystallographic analysis showed that heteroatom substituents, especially those in the 3-position on the indenyl ligand, have a substantial effect on the structure of metallocenes leading to an increase in the gap aperture in those complexes. Slippage of the indenyl fragments toward η 3-bonding was found to correlate with the electron donating ability of the substituent in the 3-position, being larger for amino than alkoxy substituents. Based upon the amount of slippage, 3-amino-substituted indenyl complexes bear strong resemblance to a fluorenyl complexes.