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Aminofluorenyl−Pentamethylcyclopentadienyl and Bis(aminofluorenyl) Derivatives of Group 4 Metals

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. http://resolver.caltech.edu/CaltechAUTHORS:20170524-154233004

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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.


Item Type:Article
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URLURL TypeDescription
http://dx.doi.org/10.1021/om000723rDOIArticle
http://pubs.acs.org/doi/abs/10.1021/om000723rPublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/om000723rPublisherSupporting Information
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.
Funders:
Funding AgencyGrant Number
Department of Energy (DOE)DE-FG03-88ER13431
National Defense Science and Engineering Graduate (NDSEG) FellowshipUNSPECIFIED
Record Number:CaltechAUTHORS:20170524-154233004
Persistent URL:http://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:25 May 2017 19:05

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