An inverted-sandwich diuranium μ-η5:η5-cyclo-P5 complex supported by U-P5 δ-bonding

Gardner, Benedict M. and Tuna, Floriana and McInnes, Eric J.L. and McMaster, Jonathan and Lewis, William and Blake, Alexander J. and Liddle, Stephen T. (2015) An inverted-sandwich diuranium μ-η5:η5-cyclo-P5 complex supported by U-P5 δ-bonding. Angewandte Chemie International Edition, 54 (24). pp. 7068-7072. ISSN 1521-3773

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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.

Item Type: Article
Keywords: cyclo-P5; density functional theory; phosphorus; uranium; δ bonding
Schools/Departments: University of Nottingham, UK > Faculty of Science > School of Chemistry
Identification Number: 10.1002/anie.201501728
Depositing User: Lewis, William
Date Deposited: 28 Sep 2017 10:39
Last Modified: 14 Oct 2017 08:31
URI: http://eprints.nottingham.ac.uk/id/eprint/46638

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