@article { , 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}, 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.}, doi = {10.1002/anie.201404898}, eissn = {1521-3773}, issn = {1433-7851}, issue = {35}, journal = {Angewandte Chemie International Edition}, pages = {9356-9359}, publicationstatus = {Published}, publisher = {Wiley}, url = {https://nottingham-repository.worktribe.com/output/733855}, volume = {53}, keyword = {amides, carbenes, ketimides, N ligands, thorium}, year = {2014}, author = {Lu, Erli and Lewis, William and Blake, Alexander J. and Liddle, Stephen T.} }