Thorium mono- and bis(imido) complexes made by reprotonation of cyclo-metalated amides

Bell, N. L. , Maron, L. and Arnold, P. L. (2015) Thorium mono- and bis(imido) complexes made by reprotonation of cyclo-metalated amides. Journal of the American Chemical Society, 137(33), pp. 10492-10495. (doi: 10.1021/jacs.5b06630) (PMID:26244991)

Abstract

Molecules containing actinide–nitrogen multiple bonds are of current interest as simple models for new actinide nitride nuclear fuels, and for their potential for the catalytic activation of inert hydrocarbon C–H bonds. Complexes with up to three uranium–nitrogen double bonds are now being widely studied, yet those with one thorium–nitrogen double bond are rare, and those with two are unknown. A new, simple mono(imido) thorium complex and the first bis(imido) thorium complex, K[Th(═NAr)N″3] and K2[Th(═NAr)2N″2], are readily made from insertion reactions (Ar = aryl, N″ = N(SiMe3)2) into the Th–C bond of the cyclometalated thorium amides [ThN″2(N(SiMe3)(SiMe2CH2))] and K[ThN″(N(SiMe3)(SiMe2CH2))2]. X-ray and computational structural analyses show a “transition-metal-like” cis-bis(imido) geometry and polarized Th═N bonds with twice the Wiberg bond order of the formally single Th–N bond in the same molecule.

• Item Type: Articles
• Additional Information: P.L.A. thanks the Technische Universitat Mu ̈ ̈ nchen − Institute for Advanced Study, funded by the German Excellence Initiative; PLA and NLB thank the University of Edinburgh, the Engineering and Physical Sciences Research Council EPSRC, and Dr Christos Apostolidis, Institute of Transuranic Elements, ITU KIT, Germany; LM thanks the Institut Universitaire de France, Humboldt Foundation, CINES, and CalMip.
• Status: Published
• Refereed: Yes
• Glasgow Author(s) Enlighten ID: Bell, Dr Nicola
• Authors: Bell, N. L., Maron, L., and Arnold, P. L.
• College/School: College of Science and Engineering > School of Chemistry
• Journal Name: Journal of the American Chemical Society
• Publisher: American Chemical Society
• ISSN: 0002-7863
• ISSN (Online): 1520-5126
• Published Online: 05 August 2015
• Copyright Holders: Copyright © 2015 American Chemical Society
• First Published: First published in Journal of the American Chemical Society 137(33): 10492-10495
• Publisher Policy: Reproduced under a Creative Commons License
• Data DOI: 10.7488/ds/289