Wildman, Elizabeth P. and Balazs, Gabor and Wooles, Ashley J. and Scheer, Manfred and Liddle, Stephen T. (2016) Thorium-phosphorus triamidoamine complexes containing Th-P single- and multiple-bond interactions. NATURE COMMUNICATIONS, 7: 12884. ISSN 2041-1723,
Full text not available from this repository. (Request a copy)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.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | RAY-ABSORPTION SPECTROSCOPY; ACTINIDE PHOSPHINIDENE COMPLEXES; DENSITY-FUNCTIONAL THEORY; URANYL-ION; URANIUM COMPLEXES; CARBENE COMPLEXES; ELECTRONIC-STRUCTURE; IMIDO ANALOGS; REACTIVITY; LIGAND; |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie > Chair Prof. Dr. Manfred Scheer |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 04 Apr 2019 11:33 |
| Last Modified: | 04 Apr 2019 11:33 |
| URI: | https://pred.uni-regensburg.de/id/eprint/3376 |
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