A Sacrificial Iminato Ligand in the Catalytic Cyanosilylation of Ketones Promoted by Organoactinide Complexes.

Four new complexes containing the bis(pentamethylcyclopentadienyl)thorium(IV) moiety, Cp* 2 Th( L1 )(Me) ( Th2 ), Cp* 2 Th( L2 )(Me) ( Th3 ), Cp* 2 Th( L1 )Cl ( Th5 ), and Cp* 2 Th( L2 )Cl ( Th6 ), were synthesized in quantitative yields via the protonolysis reaction of the metallocene precursor complexes Cp* 2 Th(Me) 2 ( Th1 ) and Cp* 2 Th(Me)Cl ( Th4 ) and the respective six- and seven-membered N-heterocyclic neutral imine ligands L1H and L2H . The molecular structures of all the complexes were established by single-crystal X-ray structure analyses. The synthesized complexes along with the precursor complexes were employed as catalysts for the cyanosilylation reaction of ketones with trimethylsilyl cyanide (Me 3 SiCN). The removal of the iminato ligand is necessary to trigger the reaction, allowing the formation of the active catalyst.