Thorium-phosphorus triamidoamine complexes containing Th-P single- and multiple-bond interactions.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 27682617.
- Also identified by DOI 10.1038/ncomms12884 and PMC identifier 5056418.
- Licence recorded as CC BY.
- The licence permits redistribution, so the abstract is shown in full and the full text is available from the publisher.
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-PH<sub>2</sub>), 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.