Benedict M. Gardner
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
Floriana Tuna
Eric J.L. McInnes
JONATHAN MCMASTER Jonathan.McMaster@nottingham.ac.uk
Professor of Chemistry
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 | https://nottingham-repository.worktribe.com/output/750481 |
Publisher URL | http://onlinelibrary.wiley.com/doi/10.1002/anie.201501728/abstract |
Contract Date | Sep 28, 2017 |
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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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