Actinide-Pnictide Chemistry: A Uranium Primary Alkyl Stibinide and a Diuranium Hexaantimonide-Tetralithium Zintl Cluster

Thomas Rookes, Gábor Balázs, Benedict Gardner, Ashley J Wooles, Manfred Scheer, Stephen Liddle

Research output: Contribution to journalArticlepeer-review

Abstract

Structurally characterised U-Sb bonds are rare. Here, we report the synthesis and characterisation of [U(TrenDMBS){Sb(H)C(H)(SiMe3)2}] (5, TrenDMBS = N(CH2CH2NSiMe2But)3) and [{U(TrenTIPS)}2{Sb3(µ6-Li)(µLi[THF]2)3Sb3}] (6, TrenTIPS = N(CH2CH2NSiPri3)3). Complex 5 is an unprecedented primary stibinide actinide complex and 6 can be formulated as containing a unique triple decker 20 skeletal-electron distorted closo tricapped Zintl cluster (Sb3Li4Sb3)2- that is analogous to the D3h closo tricapped trigonal prism form of [Ge9]2-. Quantum chemical calculations emphasise polar U-Sb bonding in 5 and 6, and that viewing (Sb3Li4Sb3)2- as a single unit rather than two distinct but contiguous (Sb3)3- units, themselves unprecedented in molecular actinide chemistry, is valid due to the presence of three weak (Sb3)···(Sb3) (3, -1)-bond critical points. Complexes 5 and 6 highlight the challenges of preparing polar U-Sb bonds and the underlying tendency for unpredictable cluster formation with Sb.
Original languageEnglish
Article numbere202300067
JournalChemistryEurope
Volume1
Issue number3
Early online date2 Oct 2023
DOIs
Publication statusPublished - 27 Nov 2023

Keywords

  • Antimony
  • Antimonide
  • Stibinide
  • Uranium
  • Zintl cluster

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