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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; Lewis, William; Blake, Alexander J.; Liddle, Stephen T.

Authors

Erli Lu

William Lewis

Alexander J. Blake

Stephen T. Liddle



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.

Citation

Lu, E., Lewis, W., Blake, A. J., & Liddle, S. 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), 9356-9359. https://doi.org/10.1002/anie.201404898

Journal Article Type Article
Acceptance Date Jul 7, 2014
Online Publication Date Jul 7, 2014
Publication Date Aug 25, 2014
Deposit Date Sep 28, 2017
Publicly Available Date Sep 28, 2017
Journal Angewandte Chemie International Edition
Print ISSN 1433-7851
Electronic ISSN 1521-3773
Publisher Wiley
Peer Reviewed Peer Reviewed
Volume 53
Issue 35
Pages 9356-9359
DOI https://doi.org/10.1002/anie.201404898
Keywords amides; carbenes; ketimides; N ligands; thorium
Public URL http://eprints.nottingham.ac.uk/id/eprint/46640
Publisher URL http://onlinelibrary.wiley.com/doi/10.1002/anie.201404898/abstract
Copyright Statement Copyright information regarding this work can be found at the following address: http://creativecommons.org/licenses/by/4.0

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Copyright Statement
Copyright information regarding this work can be found at the following address: http://creativecommons.org/licenses/by/4.0





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