The Ketimide Ligand is Not Just an Inert Spectator: Heteroallene Insertion Reactivity of an Actinide–Ketimide Linkage in a Thorium Carbene Amide Ketimide Complex
作者： Erli Lu , William Lewis , Alexander J. Blake , Stephen T. Liddle
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摘要: The ketimide anion R2C[DOUBLE BOND]N− is an important class of chemically robust ligand that binds strongly to metal ions and considered ideal for supporting reactive fragments due its inert spectator nature; this contrasts with R2N− amides exhibit a wide range reactivities. Here, we report the synthesis characterization rare example actinide 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 Th[BOND]Nketimide linkages, thereby presenting opportunity probe preferential reactivity these linkages. Importantly, studies unsaturated substrates shows insertion reactions occur preferentially at bond rather than BOND]Ccarbene or bonds. This overturns established view metal-ketimide linkages are purely spectators.
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