Reactions of a cerium(iii) amide with heteroallenes: insertion, silyl-migration and de-insertion

Abstract

Reactions of Ce[N(SiMe₃)Ph^F]₃ (–Ph^F = pentafluorophenyl) toward small molecules of the type E₁CE₂ (E₁, E₂ = O, S, NR), including carbon disulfide, carbodiimide, carbon dioxide, isocyanate and isothiocyanate are reported, resulting in distinct products, including cerium(III) dithiocarbamate, cerium(III) guanidinate, isocyanates and unsymmetric carbodiimides. These reactions were rationalized as three consecutive stages of the same reaction pathway: insertion, silyl-migration and de-insertion.