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

Author:

Rookes Thomas M.1,Balázs Gábor2,Gardner Benedict M.1,Wooles Ashley J.1,Scheer Manfred2,Liddle Stephen T.1ORCID

Affiliation:

1. Department of Chemistry The University of Manchester Oxford Road Manchester M13 9PL UK

2. Institute of Inorganic Chemistry University of Regensburg Universitätsstr. 31 93053 Regensburg Germany

Abstract

AbstractStructurally characterised U−Sb bonds are rare. Here, the synthesis and characterisation of [U(TrenDMBS){Sb(H)C(H)(SiMe3)2}] (5, TrenDMBS=N(CH2CH2NSiMe2But)3) and [{U(TrenTIPS)}2{Sb36‐Li)(μ‐Li[THF]2)3Sb3}] (6, TrenTIPS=N(CH2CH2NSiPri3)3) are reported. 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.

Funder

European Research Council

Deutsche Forschungsgemeinschaft

University of Manchester

Publisher

Wiley

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