The ketimide ligand is not just an inert spectator: heteroallene insertion reactivity of an actinide-ketimide linkage in a thorium carbene amide ketimide complex

Lu, Erli and Lewis, William and Blake, Alexander J. and Liddle, Stephen T. (2014) The ketimide ligand is not just an inert spectator: heteroallene insertion reactivity of an actinide-ketimide linkage in a thorium carbene amide ketimide complex. Angewandte Chemie International Edition, 53 (35). pp. 9356-9359. ISSN 1521-3773

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Abstract

The ketimide anion R2C[DOUBLE BOND]N− is an important class of chemically robust ligand that binds strongly to metal ions and is considered ideal for supporting reactive metal fragments due to its inert spectator nature; this contrasts with R2N− amides that exhibit a wide range of reactivities. Here, we report the synthesis and characterization of a rare example of an actinide ketimide complex [Th(BIPMTMS){N(SiMe3)2}(N[DOUBLE BOND]CPh2)] [2, BIPMTMS=C(PPh2NSiMe3)2]. Complex 2 contains Th[DOUBLE BOND]Ccarbene, Th[BOND]Namide and Th[BOND]Nketimide linkages, thereby presenting the opportunity to probe the preferential reactivity of these linkages. Importantly, reactivity studies of 2 with unsaturated substrates shows that insertion reactions occur preferentially at the Th[BOND]Nketimide bond rather than at the Th[DOUBLE BOND]Ccarbene or Th[BOND]Namide bonds. This overturns the established view that metal-ketimide linkages are purely inert spectators.

Item Type: Article
Keywords: amides; carbenes; ketimides; N ligands; thorium
Schools/Departments: University of Nottingham, UK > Faculty of Science > School of Chemistry
Identification Number: 10.1002/anie.201404898
Depositing User: Lewis, William
Date Deposited: 28 Sep 2017 12:05
Last Modified: 14 Oct 2017 08:28
URI: http://eprints.nottingham.ac.uk/id/eprint/46640

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