Miller, Stephen A. and Bercaw, John E. (2000) Aminofluorenyl−Pentamethylcyclopentadienyl and Bis(aminofluorenyl) Derivatives of Group 4 Metals. Organometallics, 19 (26). pp. 5608-5613. ISSN 0276-7333. doi:10.1021/om000723r. https://resolver.caltech.edu/CaltechAUTHORS:20170524-154233004
Use this Persistent URL to link to this item: https://resolver.caltech.edu/CaltechAUTHORS:20170524-154233004
Abstract
New group 4 compounds containing a 9-(dialkylamino)fluorenyl ligand have been prepared, and their properties and reactivities have been briefly investigated. Single-crystal X-ray analysis of {9-(N,N-dimethylamino)fluorenyl}_2ZrCl_2 (4) reveals strong zirconium−nitrogen dative bonds. The asymmetric unit contains two molecules with an unusual coordination of aminofluorenyl ligands, best described as comprised of a strong Zr−N dative interaction and essentially an η^1-fluorenyl coordination, supplemented by a weak additional C C dative interaction of one double bond of one of the benzo units. The barrier to rotation around the C−N bond of {9-(N,N-diisopropylamino)fluorenyl}(pentamethylcyclopentadienyl)ZrCl_2 (9) has been determined: ΔG⧧(−25 °C) = 11.1 kcal·mol^(-1). Unlike related aminoborollide complexes, aminofluorenyl complexes resist quaternization by alkyl halides. Several aminofluorenyl complexes have been tested for propylene polymerization behavior in the presence of methylaluminoxane (MAO); atactic polypropylene is obtained with very low activities. The syntheses of 9-(dialkylamino)fluorene compounds are described, as are the syntheses of group 4 compounds via the corresponding 9-(dialkylamino)fluorenide lithium salts.
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Additional Information: | © 2000 American Chemical Society. Received August 18, 2000. Publication Date (Web): November 16, 2000. This work has been funded by the USDOE Office of Basic Energy Sciences (Grant No. DE-FG03-88ER13431) and by a DOD National Defense Science and Engineering Fellowship awarded to S.M. The authors thank Dr. Michael Day and Mr. Lawrence Henling for obtaining the X-ray crystal structure. | ||||||||||||
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Issue or Number: | 26 | ||||||||||||
DOI: | 10.1021/om000723r | ||||||||||||
Record Number: | CaltechAUTHORS:20170524-154233004 | ||||||||||||
Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20170524-154233004 | ||||||||||||
Official Citation: | Aminofluorenyl−Pentamethylcyclopentadienyl and Bis(aminofluorenyl) Derivatives of Group 4 Metals Stephen A. Miller and John E. Bercaw Organometallics 2000 19 (26), 5608-5613 DOI: 10.1021/om000723r | ||||||||||||
Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | ||||||||||||
ID Code: | 77733 | ||||||||||||
Collection: | CaltechAUTHORS | ||||||||||||
Deposited By: | Tony Diaz | ||||||||||||
Deposited On: | 25 May 2017 19:05 | ||||||||||||
Last Modified: | 15 Nov 2021 17:33 |
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