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- Title
Actinide–Pnictide (An−Pn) Bonds Spanning Non‐Metal, Metalloid, and Metal Combinations (An=U, Th; Pn=P, As, Sb, Bi).
- Authors
Rookes, Thomas M.; Wildman, Elizabeth P.; Gardner, Benedict M.; Wooles, Ashley J.; Gregson, Matthew; Tuna, Floriana; Liddle, Stephen T.; Balázs, Gábor; Scheer, Manfred
- Abstract
Abstract: The synthesis and characterisation is presented of the compounds [An(TrenDMBS){Pn(SiMe3)2}] and [An(TrenTIPS){Pn(SiMe3)2}] [TrenDMBS=N(CH2CH2NSiMe2But)3, An=U, Pn=P, As, Sb, Bi; An=Th, Pn=P, As; TrenTIPS=N(CH2CH2NSiPri3)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.
- Subjects
ACTINIDE elements; SEMIMETALS; METAL-metal bonds; THORIUM; URANIUM; THERMOLYSIS; PHOTOLYSIS (Chemistry)
- Publication
Angewandte Chemie, 2018, Vol 130, Issue 5, p1346
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.201711824