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.

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