An Inverted‐Sandwich Diuranium μ‐η5:η5‐Cyclo‐P5 Complex Supported by U‐P5 δ‐Bonding |
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| Authors: | Dr Benedict M Gardner Dr Floriana Tuna Prof Eric J L McInnes Dr Jonathan McMaster Dr William Lewis Prof Alexander J Blake Prof Stephen T Liddle |
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| Institution: | 1. School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD (UK);2. School of Chemistry and Photon Science Institute, University of Manchester, Oxford Road, Manchester, M13 9PL (UK) |
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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. |
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| Keywords: | cyclo‐P5 density functional theory phosphorus uranium δ bonding |
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