Rookes, Thomas M. and Wildman, Elizabeth P. and Balazs, Gabor and Gardner, Benedict M. and Wooles, Ashley J. and Gregson, Matthew and Tuna, Floriana and Scheer, Manfred and Liddle, Stephen T. (2018) Actinide-Pnictide (An-Pn) Bonds Spanning Non-Metal, Metalloid, and Metal Combinations (An=U, Th; Pn=P, As, Sb, Bi). ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 57 (5). pp. 1332-1336. ISSN 1433-7851, 1521-3773
Full text not available from this repository. (Request a copy)Abstract
The synthesis and characterisation is presented of the compounds [An(Tren(DMBS)){Pn(SiMe3)(2)}] and [An(Tren(TIPS)){Pn(SiMe3)(2)}] [Tren(DMBS)=N(CH2CH2NSiMe2But)(3), An=U, Pn=P, As, Sb, Bi; An=Th, Pn=P, As; Tren(TIPS)=N(CH2CH2NSiPr3i)(3), An=U, Pn=P, As, Sb; An=Th, Pn=P, As, Sb]. The U-Sb and Th-Sb moieties are unprecedented examples of any kind of An-Sb molecular bond, and the U-Bi bond is the first two-centre-two-electron (2c-2e) one. The Th-Bi combination was too unstable to isolate, underscoring the fragility of these linkages. However, the U-Bi complex is the heaviest 2c-2e pairing of two elements involving an actinide on a macroscopic scale under ambient conditions, and this is exceeded only by An-An pairings prepared under cryogenic matrix isolation conditions. Thermolysis and photolysis experiments suggest that the U-Pn bonds degrade by homolytic bond cleavage, whereas the more redox-robust thorium compounds engage in an acid-base/dehydrocoupling route.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | URANIUM HYDRIDE MOLECULES; PHOSPHINIDENE COMPLEXES; CRYSTAL-STRUCTURE; TRIMETHYLSILYL DERIVATIVES; INTERMETALLOID CLUSTERS; THEORETICAL EVIDENCE; ZINTL ANION; VB-ELEMENTS; CHEMISTRY; REACTIVITY; metalloids; metal-metal bonds; pnictides; thorium; 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: | 20 Mar 2020 14:56 |
| Last Modified: | 20 Mar 2020 14:56 |
| URI: | https://pred.uni-regensburg.de/id/eprint/15176 |
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