Actinide–Pnictide (An−Pn) Bonds Spanning Non‐Metal,Metalloid, and Metal Combinations (An=U,Th; Pn=P,As, Sb,Bi) |
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| Authors: | Thomas M. Rookes Dr. Elizabeth P. Wildman Dr. Gábor Balázs Dr. Benedict M. Gardner Dr. Ashley J. Wooles Dr. Matthew Gregson Dr. Floriana Tuna Prof. Dr. Manfred Scheer Prof. Dr. Stephen T. Liddle |
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| Affiliation: | 1. School of Chemistry, The University of Manchester, Manchester, UK;2. Institute of Inorganic Chemistry, University of Regensburg, Regensburg, Germany |
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| 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. |
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| Keywords: | metalloids metal– metal bonds pnictides thorium uranium |
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