Erli Lu
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
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 | https://nottingham-repository.worktribe.com/output/733855 |
Publisher URL | http://onlinelibrary.wiley.com/doi/10.1002/anie.201404898/abstract |
Contract Date | Sep 28, 2017 |
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