The ketimide ligand is not just an inert spectator: heteroallene insertion reactivity of an actinide-ketimide linkage in a thorium carbene amide ketimide complex
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...
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Wiley-VCH Verlag
2014
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| Online Access: | https://eprints.nottingham.ac.uk/46640/ |
| _version_ | 1848797374851317760 |
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| author | Lu, Erli Lewis, William Blake, Alexander J. Liddle, Stephen T. |
| author_facet | Lu, Erli Lewis, William Blake, Alexander J. Liddle, Stephen T. |
| author_sort | Lu, Erli |
| building | Nottingham Research Data Repository |
| collection | Online Access |
| description | 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. |
| first_indexed | 2025-11-14T20:02:52Z |
| format | Article |
| id | nottingham-46640 |
| institution | University of Nottingham Malaysia Campus |
| institution_category | Local University |
| last_indexed | 2025-11-14T20:02:52Z |
| publishDate | 2014 |
| publisher | Wiley-VCH Verlag |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | nottingham-466402020-05-04T16:52:08Z https://eprints.nottingham.ac.uk/46640/ 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. 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. Wiley-VCH Verlag 2014-08-25 Article PeerReviewed Lu, Erli, Lewis, William, 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 amides; carbenes; ketimides; N ligands; thorium http://onlinelibrary.wiley.com/doi/10.1002/anie.201404898/abstract doi:10.1002/anie.201404898 doi:10.1002/anie.201404898 |
| spellingShingle | amides; carbenes; ketimides; N ligands; thorium Lu, Erli Lewis, William Blake, Alexander J. Liddle, Stephen T. The ketimide ligand is not just an inert spectator: heteroallene insertion reactivity of an actinide-ketimide linkage in a thorium carbene amide ketimide complex |
| title | The ketimide ligand is not just an inert spectator: heteroallene insertion reactivity of an actinide-ketimide linkage in a thorium carbene amide ketimide complex |
| title_full | The ketimide ligand is not just an inert spectator: heteroallene insertion reactivity of an actinide-ketimide linkage in a thorium carbene amide ketimide complex |
| title_fullStr | The ketimide ligand is not just an inert spectator: heteroallene insertion reactivity of an actinide-ketimide linkage in a thorium carbene amide ketimide complex |
| title_full_unstemmed | The ketimide ligand is not just an inert spectator: heteroallene insertion reactivity of an actinide-ketimide linkage in a thorium carbene amide ketimide complex |
| title_short | The ketimide ligand is not just an inert spectator: heteroallene insertion reactivity of an actinide-ketimide linkage in a thorium carbene amide ketimide complex |
| title_sort | ketimide ligand is not just an inert spectator: heteroallene insertion reactivity of an actinide-ketimide linkage in a thorium carbene amide ketimide complex |
| topic | amides; carbenes; ketimides; N ligands; thorium |
| url | https://eprints.nottingham.ac.uk/46640/ https://eprints.nottingham.ac.uk/46640/ https://eprints.nottingham.ac.uk/46640/ |