Actinide Pnictinidene Chemistry: A Terminal Thorium Parent Arsinidene Complex Stabilised by a Super Bulky Triamidoamine Ligand

Jingzhen Du, Gábor Baláȥs, John A. Seed, Jonathan D. Cryer, Ashley J. Wooles, Manfred Scheer, Stephen Liddle

Research output: Contribution to journalArticlepeer-review

Abstract

We report the direct synthesis of the terminal pnictidenes [An(Tren TCHS )(PnH)][M(2,2,2-cryptand)] (Tren TCHS = {N(CH 2 CH 2 NSiCy 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(Tren TCHS )(PnH 2 )] (An/Pn = Th/P 9 , Th/As 10 , U/P 11 , U/As 12 ). Use of the super-bulky Tren TCHS 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(Tren TIPS ){μ-As(H)K(15-crown-5)}] (Tren TIPS = {N(CH2 CH2 NSiPr i3 )} 3- ) reveals a stronger Th-As bond in the former compared to the latter, as expected, but 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.
Original languageEnglish
JournalAngewandte Chemie International Edition
Early online date18 Oct 2022
DOIs
Publication statusE-pub ahead of print - 18 Oct 2022

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