Journal
NATURE COMMUNICATIONS
Volume 8, Issue -, Pages -Publisher
NATURE PUBLISHING GROUP
DOI: 10.1038/ncomms14769
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Funding
- Royal Society [UF110005]
- European Research Council [239621, 612724]
- Engineering and Physical Sciences Research Council [EP/G051763/1, EP/M027015/1]
- University of Nottingham
- Deutsche Forschungsgemeinschaft
- COST Action [CM1006]
- University of Manchester
- University of Regensburg
- Engineering and Physical Sciences Research Council [EP/G051763/1, EP/M027015/1] Funding Source: researchfish
- Royal Society [UF110005] Funding Source: Royal Society
- EPSRC [EP/G051763/1, EP/M027015/1] Funding Source: UKRI
- European Research Council (ERC) [239621, 612724] Funding Source: European Research Council (ERC)
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Despite a major expansion of uranium-ligand multiple bond chemistry in recent years, analogous complexes involving other actinides (An) remain scarce. For thorium, under ambient conditions only a few multiple bonds to carbon, nitrogen, phosphorus and chalcogenides are reported, and none to arsenic are known; indeed only two complexes with thorium-arsenic single bonds have been structurally authenticated, reflecting the challenges of stabilizing polar linkages at the large thorium ion. Here, we report thorium parent-arsenide (ThAsH2), -arsinidiides (ThAs(H)K and ThAs(H)Th) and arsenido (ThAsTh) linkages stabilized by a bulky triamidoamine ligand. The ThAs(H)K and ThAsTh linkages exhibit polarized-covalent thorium-arsenic multiple bonding interactions, hitherto restricted to cryogenic matrix isolation experiments, and the AnAs(H) An and AnAsAn linkages reported here have no precedent in f-block chemistry. 7s, 6d and 5f orbital contributions to the Th-As bonds are suggested by quantum chemical calculations, and their compositions unexpectedly appear to be tensioned differently compared to phosphorus congeners.
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