Thorium–phosphorus triamidoamine complexes containing Th–P single- and multiple-bond interactions
Abstract Despite the burgeoning field of uranium-ligand multiple bonds, analogous complexes involving other actinides remain scarce. For thorium, under ambient conditions only a few multiple bonds to carbon, nitrogen, oxygen, sulfur, selenium and tellurium are reported, and no multiple bonds to phos...
| Main Authors: | , , , , |
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2016-09-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/ncomms12884 |
| _version_ | 1797811427190243328 |
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| author | Elizabeth P. Wildman Gábor Balázs Ashley J. Wooles Manfred Scheer Stephen T. Liddle |
| author_facet | Elizabeth P. Wildman Gábor Balázs Ashley J. Wooles Manfred Scheer Stephen T. Liddle |
| author_sort | Elizabeth P. Wildman |
| collection | DOAJ |
| description | Abstract Despite the burgeoning field of uranium-ligand multiple bonds, analogous complexes involving other actinides remain scarce. For thorium, under ambient conditions only a few multiple bonds to carbon, nitrogen, oxygen, sulfur, selenium and tellurium are reported, and no multiple bonds to phosphorus are known, reflecting a general paucity of synthetic methodologies and also problems associated with stabilising these linkages at the large thorium ion. Here we report structurally authenticated examples of a parent thorium(IV)–phosphanide (Th–PH2), a terminal thorium(IV)–phosphinidene (Th=PH), a parent dithorium(IV)–phosphinidiide (Th–P(H)-Th) and a discrete actinide–phosphido complex under ambient conditions (Th=P=Th). Although thorium is traditionally considered to have dominant 6d-orbital contributions to its bonding, contrasting to majority 5f-orbital character for uranium, computational analyses suggests that the bonding of thorium can be more nuanced, in terms of 5f- versus 6d-orbital composition and also significant involvement of the 7s-orbital and how this affects the balance of 5f- versus 6d-orbital bonding character. |
| first_indexed | 2024-03-13T07:23:31Z |
| format | Article |
| id | doaj.art-a8c04fbc074b48debf57a62235732ee3 |
| institution | Directory Open Access Journal |
| issn | 2041-1723 |
| language | English |
| last_indexed | 2024-03-13T07:23:31Z |
| publishDate | 2016-09-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj.art-a8c04fbc074b48debf57a62235732ee32023-06-04T11:32:06ZengNature PortfolioNature Communications2041-17232016-09-017111110.1038/ncomms12884Thorium–phosphorus triamidoamine complexes containing Th–P single- and multiple-bond interactionsElizabeth P. Wildman0Gábor Balázs1Ashley J. Wooles2Manfred Scheer3Stephen T. Liddle4School of Chemistry, The University of ManchesterInstitute of Inorganic Chemistry, University of RegensburgSchool of Chemistry, The University of ManchesterInstitute of Inorganic Chemistry, University of RegensburgSchool of Chemistry, The University of ManchesterAbstract Despite the burgeoning field of uranium-ligand multiple bonds, analogous complexes involving other actinides remain scarce. For thorium, under ambient conditions only a few multiple bonds to carbon, nitrogen, oxygen, sulfur, selenium and tellurium are reported, and no multiple bonds to phosphorus are known, reflecting a general paucity of synthetic methodologies and also problems associated with stabilising these linkages at the large thorium ion. Here we report structurally authenticated examples of a parent thorium(IV)–phosphanide (Th–PH2), a terminal thorium(IV)–phosphinidene (Th=PH), a parent dithorium(IV)–phosphinidiide (Th–P(H)-Th) and a discrete actinide–phosphido complex under ambient conditions (Th=P=Th). Although thorium is traditionally considered to have dominant 6d-orbital contributions to its bonding, contrasting to majority 5f-orbital character for uranium, computational analyses suggests that the bonding of thorium can be more nuanced, in terms of 5f- versus 6d-orbital composition and also significant involvement of the 7s-orbital and how this affects the balance of 5f- versus 6d-orbital bonding character.https://doi.org/10.1038/ncomms12884 |
| spellingShingle | Elizabeth P. Wildman Gábor Balázs Ashley J. Wooles Manfred Scheer Stephen T. Liddle Thorium–phosphorus triamidoamine complexes containing Th–P single- and multiple-bond interactions Nature Communications |
| title | Thorium–phosphorus triamidoamine complexes containing Th–P single- and multiple-bond interactions |
| title_full | Thorium–phosphorus triamidoamine complexes containing Th–P single- and multiple-bond interactions |
| title_fullStr | Thorium–phosphorus triamidoamine complexes containing Th–P single- and multiple-bond interactions |
| title_full_unstemmed | Thorium–phosphorus triamidoamine complexes containing Th–P single- and multiple-bond interactions |
| title_short | Thorium–phosphorus triamidoamine complexes containing Th–P single- and multiple-bond interactions |
| title_sort | thorium phosphorus triamidoamine complexes containing th p single and multiple bond interactions |
| url | https://doi.org/10.1038/ncomms12884 |
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