1. Actinide Pnictinidene Chemistry: A Terminal Thorium Parent-Arsinidene Complex Stabilised by a Super-Bulky Triamidoamine Ligand.
- Author
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Du J, Balázs G, Seed JA, Cryer JD, Wooles AJ, Scheer M, and Liddle ST
- Abstract
We report the direct synthesis of the terminal pnictidenes [An(Tren
TCHS )(PnH)][M(2,2,2-cryptand)] (TrenTCHS ={N(CH2 CH2 NSiCy3 )3 }3- ; An/Pn/M=Th/P/Na 5, Th/As/K 6, U/P/Na 7, U/As/K 8) and their conversion to the pnictides [An(TrenTCHS )(PnH2 )] (An/Pn=Th/P 9, Th/As 10, U/P 11, U/As 12). Use of the super-bulky TrenTCHS ligand was essential to accessing complete families, and 6 is an unprecedented example of a terminal thorium-arsinidene complex and only the second structurally authenticated parent terminal arsinidene complex of any metal. Comparison of the terminal Th=AsH unit of 6 to the bridging ThAs(H)K linkage in structurally analogous [Th(TrenTIPS ){μ-As(H)K(15-crown-5)}] (TrenTIPS ={N(CH2 CH2 NSiPri 3 )3 }3- ) reveals a stronger Th-As bond in the former compared to the latter, and a large response overall to the nature of the Th=AsH bonding upon removal of the electrostatically-bound K-ion; the σ-bond changes little but the π-bond is significantly perturbed., (© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)- Published
- 2022
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