Du, Jingzhen and Balazs, Gabor and Seed, John A. and Cryer, Jonathan D. and Wooles, Ashley J. and Scheer, Manfred and Liddle, Stephen T. (2022) Actinide Pnictinidene Chemistry: A Terminal Thorium Parent-Arsinidene Complex Stabilised by a Super-Bulky Triamidoamine Ligand. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 61 (50): e202211627. ISSN 1433-7851, 1521-3773
Full text not available from this repository. (Request a copy)Abstract
We report the direct synthesis of the terminal pnictidenes [An(Tren(TCHS))(PnH)][M(2,2,2-cryptand)] (Tren(TCHS)={N(CH2CH2NSiCy3)(3)}(3-); An/Pn/M=Th/P/Na 5, Th/As/K 6, U/P/Na 7, U/As/K 8) and their conversion to the pnictides [An(Tren(TCHS))(PnH(2))] (An/Pn=Th/P 9, Th/As 10, U/P 11, U/As 12). Use of the super-bulky Tren(TCHS) ligand was essential to accessing complete families, and 6 is an unprecedented example of a terminal thorium-arsinidene complex and only the second structurally authenticated parent terminal arsinidene complex of any metal. Comparison of the terminal Th=AsH unit of 6 to the bridging ThAs(H)K linkage in structurally analogous [Th(Tren(TIPS)){mu-As(H)K(15-crown-5)}] (Tren(TIPS)={N(CH2CH2NSiPr3i)(3)}(3-)) reveals a stronger Th-As bond in the former compared to the latter, and a large response overall to the nature of the Th=AsH bonding upon removal of the electrostatically-bound K-ion; the sigma-bond changes little but the pi-bond is significantly perturbed.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | RAY-ABSORPTION SPECTROSCOPY; MAIN-GROUP ELEMENTS; N BOND-CLEAVAGE; PHOSPHINIDENE COMPLEXES; ELECTRONIC-STRUCTURE; INDUCED DEGRADATION; TRANSITION-METALS; MULTIPLE BONDS; PHOSPHORUS; SINGLE; Actinides; Arsinidene; Density Functional Theory; Multiple Bonds; Phosphinidene |
| 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: | 08 Feb 2024 07:00 |
| Last Modified: | 08 Feb 2024 07:00 |
| URI: | https://pred.uni-regensburg.de/id/eprint/57392 |
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