Abstract
The ketimide anion R2C—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—CPh2)] [2, BIPMTMS=C(PPh2NSiMe3)2]. Complex 2 contains Th—Ccarbene, Th—Namide and Th—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—Nketimide bond rather than at the Th—Ccarbene or Th—Namide bonds. This overturns the established view that metal-ketimide linkages are purely inert spectators.
Highlights
The ketimide anion R2C=NÀ 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 R2NÀ amides that exhibit a wide range of reactivities
There is a crucial difference between amides and ketimides: in the former the nitrogen hybridization is sp2 or sp3 and it bears two NÀC/Si singly bonded groups, whereas in the latter the nitrogen hybridization is sp or sp2 and it is bonded to only one carbon atom with a N=C double bond
Actinide amides are less well-developed than their transition metal counterparts, they have been known for decades and their reactivity is extensively investigated.[8,9,10]
Summary
The ketimide anion R2C=NÀ 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 R2NÀ amides that exhibit a wide range of reactivities. As part of our investigations of An-ligand multiple bond chemistry,[14] we describe here the synthesis of a thorium carbene amide ketimide that features Th=Ccarbene, ThÀNamide, and ThÀNketimide bonds in one molecule.
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