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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.

Journal Article Type Article
Publication Date Aug 25, 2014
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
APA6 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
DOI https://doi.org/10.1002/anie.201404898
Keywords amides; carbenes; ketimides; N ligands; thorium
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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