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An Inverted-Sandwich Diuranium μ-η5:η5-Cyclo-P5 Complex Supported by U-P5 δ-Bonding

Gardner, Benedict M.; Tuna, Floriana; McInnes, Eric J.L.; McMaster, Jonathan; Lewis, William; Blake, Alexander J.; Liddle, Stephen T.

Authors

Benedict M. Gardner

Floriana Tuna

Eric J.L. McInnes

William Lewis

Alexander J. Blake

Stephen T. Liddle



Abstract

© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. Abstract Reaction of [U(TrenTIPS)] [1, TrenTIPS=N(CH2CH2NSiiPr3)3] with 0.25 equivalents of P4 reproducibly affords the unprecedented actinide inverted sandwich cyclo-P5 complex [{U(TrenTIPS)}2(μ-η5:η5-cyclo-P5)] (2). All prior examples of cyclo-P5 are stabilized by d-block metals, so 2 shows that cyclo-P5 does not require d-block ions to be prepared. Although cyclo-P5 is isolobal to cyclopentadienyl, which usually bonds to metals via σ- and π-interactions with minimal δ-bonding, theoretical calculations suggest the principal bonding in the U(P5)U unit is polarized δ-bonding. Surprisingly, the characterization data are overall consistent with charge transfer from uranium to the cyclo-P5 unit to give a cyclo-P5 charge state that approximates to a dianionic formulation. This is ascribed to the larger size and superior acceptor character of cyclo-P5 compared to cyclopentadienyl, the strongly reducing nature of uranium(III), and the availability of uranium δ-symmetry 5f orbitals.

Journal Article Type Article
Publication Date Jun 1, 2015
Journal Angewandte Chemie - International Edition
Print ISSN 1433-7851
Electronic ISSN 1521-3773
Publisher Wiley
Peer Reviewed Peer Reviewed
Volume 54
Issue 24
Pages 7068-7072
APA6 Citation Gardner, B. M., Tuna, F., McInnes, E. J., McMaster, J., Lewis, W., Blake, A. J., & Liddle, S. T. (2015). An Inverted-Sandwich Diuranium μ-η5:η5-Cyclo-P5 Complex Supported by U-P5 δ-Bonding. Angewandte Chemie International Edition, 54(24), 7068-7072. https://doi.org/10.1002/anie.201501728
DOI https://doi.org/10.1002/anie.201501728
Keywords cyclo-P5; density functional theory; phosphorus; uranium; δ bonding
Publisher URL http://onlinelibrary.wiley.com/doi/10.1002/anie.201501728/abstract
Copyright Statement Copyright information regarding this work can be found at the following address: http://creativecommons.org/licenses/by/4.0

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Copyright Statement
Copyright information regarding this work can be found at the following address: http://creativecommons.org/licenses/by/4.0





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