Synthesis, Characterization, and Polymerization Properties of Bis(2-menthylindenyl)zirconium Dichloride and Bis(2-menthyl-4,7-dimethylindenyl)zirconium Dichloride
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- 作者：Ronald L. Halterman ; Darryl R. Fahey ; Eric F. Bailly ; David W. Dockter ; Oleg Stenzel ; Jason L. Shipman ; Masood A. Khan ; Sebastian Dechert ; and Herbert Schumann
- 刊名：Organometallics
- 出版年：2000
- 出版时间：December 11, 2000
- 年：2000
- 卷：19
- 期：25
- 页码：5464 - 5470
- 全文大小：113K
- 年卷期：v.19,no.25(December 11, 2000)
- ISSN：1520-6041
文摘
The tetrakis(triphenylphosphine)palladium-catalyzed cross coupling of 2-bromoindene or2-bromo-4,7-dimethylindene with menthylmagnesium chloride gave the novel ligands2-menthylindene (10) and 2-menthyl-4,7-dimethylindene (11) in 66 and 57% yields. Theseindenes were deprotonated with n-BuLi to give isolated indenyllithium complexes whichwere metalated with zirconium tetrachloride to give bis(2-menthylindenyl)zirconium dichloride (14) and bis(2-menthyl-4,7-dimethylindenyl)zirconium dichloride (15) in 40 and 66%yields. Both complexes formed as their single possible stereoisomer and were characterizedby X-ray crystallography and MS, NMR, and IR spectroscopy. The variable-temperature 1HNMR spectrum of bis(2-menthyl-4,7-dimethylindenyl)zirconium dichloride (15) showed thatit interconverts with a rotational activation barrier of about 12.5 ± 0.5 kcal/mol, and thata 60:40 mixture of C2-symmetric diastereomeric conformations was present at -50 
tities/deg.gif">C. The1H NMR spectrum of bis(2-menthylindenyl)zirconium dichloride (14) was invariant between-50 and +50 tities/deg.gif">C. Complexes 14 and 15 polymerized propene in the presence of methylaluminumoxane (MAO) and hydrogen (10 960 and 33 750 g PP/g Zr h, respectively). Themolecular weights and stereoregularity of the polymers produced were low.
tities/deg.gif">C. The1H NMR spectrum of bis(2-menthylindenyl)zirconium dichloride (14) was invariant between-50 and +50 tities/deg.gif">C. Complexes 14 and 15 polymerized propene in the presence of methylaluminumoxane (MAO) and hydrogen (10 960 and 33 750 g PP/g Zr h, respectively). Themolecular weights and stereoregularity of the polymers produced were low.