Wildman, Elizabeth P. and Balazs, Gabor and Wooles, Ashley J. and Scheer, Manfred and Liddle, Stephen T. (2017) Triamidoamine thorium-arsenic complexes with parent arsenide, arsinidiide and arsenido structural motifs. NATURE COMMUNICATIONS, 8: 14769. ISSN 2041-1723,
Full text not available from this repository. (Request a copy)Abstract
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.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | MULTIPLE BONDS; MOLECULAR-COMPOUNDS; CRYSTAL-STRUCTURES; CARBENE COMPLEXES; KETIMIDE COMPLEX; INFRARED-SPECTRA; LIGAND; REACTIVITY; PHOSPHORUS; URANIUM; |
| 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: | 14 Dec 2018 13:00 |
| Last Modified: | 25 Feb 2019 11:02 |
| URI: | https://pred.uni-regensburg.de/id/eprint/225 |
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