期刊
NATURE COMMUNICATIONS
卷 7, 期 -, 页码 -出版社
NATURE RESEARCH
DOI: 10.1038/ncomms12884
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资金
- Royal Society
- European Research Council
- Engineering and Physical Sciences Research Council
- University of Nottingham
- University of Manchester
- University of Regensburg
- Deutsche Forschungsgemeinschaft
- COST Action [CM1006]
- EPSRC [EP/K024000/1, EP/M027015/1, EP/K024000/2, EP/G051763/1] Funding Source: UKRI
- Engineering and Physical Sciences Research Council [EP/M027015/1, EP/K024000/1, EP/G051763/1, EP/K024000/2] Funding Source: researchfish
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.
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