An inverted-sandwich diuranium μ-η5:η5-cyclo-P5 complex supported by U-P5 δ-bonding
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 d...
| Main Authors: | , , , , , , |
|---|---|
| Format: | Article |
| Published: |
Wiley-VCH Verlag
2015
|
| Subjects: | |
| Online Access: | https://eprints.nottingham.ac.uk/46638/ |
| _version_ | 1848797374239997952 |
|---|---|
| author | Gardner, Benedict M. Tuna, Floriana McInnes, Eric J.L. McMaster, Jonathan Lewis, William Blake, Alexander J. Liddle, Stephen T. |
| author_facet | Gardner, Benedict M. Tuna, Floriana McInnes, Eric J.L. McMaster, Jonathan Lewis, William Blake, Alexander J. Liddle, Stephen T. |
| author_sort | Gardner, Benedict M. |
| building | Nottingham Research Data Repository |
| collection | Online Access |
| description | 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. |
| first_indexed | 2025-11-14T20:02:51Z |
| format | Article |
| id | nottingham-46638 |
| institution | University of Nottingham Malaysia Campus |
| institution_category | Local University |
| last_indexed | 2025-11-14T20:02:51Z |
| publishDate | 2015 |
| publisher | Wiley-VCH Verlag |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | nottingham-466382020-05-04T17:07:21Z https://eprints.nottingham.ac.uk/46638/ 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. 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. Wiley-VCH Verlag 2015-06-01 Article PeerReviewed Gardner, Benedict M., Tuna, Floriana, McInnes, Eric J.L., McMaster, Jonathan, Lewis, William, 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 cyclo-P5; density functional theory; phosphorus; uranium; δ bonding http://onlinelibrary.wiley.com/doi/10.1002/anie.201501728/abstract doi:10.1002/anie.201501728 doi:10.1002/anie.201501728 |
| spellingShingle | cyclo-P5; density functional theory; phosphorus; uranium; δ bonding Gardner, Benedict M. Tuna, Floriana McInnes, Eric J.L. McMaster, Jonathan Lewis, William Blake, Alexander J. Liddle, Stephen T. An inverted-sandwich diuranium μ-η5:η5-cyclo-P5 complex supported by U-P5 δ-bonding |
| title | An inverted-sandwich diuranium μ-η5:η5-cyclo-P5 complex supported by U-P5 δ-bonding |
| title_full | An inverted-sandwich diuranium μ-η5:η5-cyclo-P5 complex supported by U-P5 δ-bonding |
| title_fullStr | An inverted-sandwich diuranium μ-η5:η5-cyclo-P5 complex supported by U-P5 δ-bonding |
| title_full_unstemmed | An inverted-sandwich diuranium μ-η5:η5-cyclo-P5 complex supported by U-P5 δ-bonding |
| title_short | An inverted-sandwich diuranium μ-η5:η5-cyclo-P5 complex supported by U-P5 δ-bonding |
| title_sort | inverted-sandwich diuranium μ-η5:η5-cyclo-p5 complex supported by u-p5 δ-bonding |
| topic | cyclo-P5; density functional theory; phosphorus; uranium; δ bonding |
| url | https://eprints.nottingham.ac.uk/46638/ https://eprints.nottingham.ac.uk/46638/ https://eprints.nottingham.ac.uk/46638/ |