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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.

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

Journal Article Type Article
Acceptance Date Feb 23, 2015
Online Publication Date Apr 27, 2015
Publication Date Jun 1, 2015
Deposit Date Sep 28, 2017
Publicly Available Date Sep 28, 2017
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
DOI https://doi.org/10.1002/anie.201501728
Keywords cyclo-P5; density functional theory; phosphorus; uranium; δ bonding
Public URL http://eprints.nottingham.ac.uk/id/eprint/46638
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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