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The Ketimide Ligand is Not Just an Inert Spectator: Heteroallene Insertion Reactivity of an Actinide–Ketimide Linkage in a Thorium Carbene Amide Ketimide Complex
Author(s) -
Lu Erli,
Lewis William,
Blake Alexander J.,
Liddle Stephen T.
Publication year - 2014
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201404898
Subject(s) - carbene , reactivity (psychology) , amide , chemistry , actinide , ligand (biochemistry) , inert , metal , medicinal chemistry , thorium , stereochemistry , catalysis , inorganic chemistry , organic chemistry , materials science , medicine , biochemistry , alternative medicine , receptor , uranium , pathology , metallurgy
Abstract The ketimide anion R 2 CN − 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 R 2 N − 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(BIPM TMS ){N(SiMe 3 ) 2 }(NCPh 2 )] [ 2 , BIPM TMS =C(PPh 2 NSiMe 3 ) 2 ]. Complex 2 contains ThC carbene , ThN amide and ThN ketimide 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 ThN ketimide bond rather than at the ThC carbene or ThN amide bonds. This overturns the established view that metal‐ketimide linkages are purely inert spectators.