B(C 6 F 5 ) 3 ‐Mediated Transformations and Hydrogenation of Carbodiimides

The reactivity of a series of carbodiimides RNCNR (R= t Bu ( 1 a ), i Pr ( 1 b ), SiMe 3 ( 1 c ), and Dipp (2,6‐di‐ iso ‐propylphenyl ( 1 d )) with B(C 6 F 5 ) 3 was investigated. After initial adduct formation, several distinct reaction pathways were identified. These pathways involve either isomerization of the carbodiimide to cyanamide derivatives or insertion of a carbodiimide into a BC bond of B(C 6 F 5 ) 3 to yield four‐membered heterocycles. In the presence of dihydrogen, stepwise hydrogenation of the heteroallene moiety in the carbodiimides was achieved, which yielded the respective amidine–B(C 6 F 5 ) 3 adducts and amidinium borate salts upon reaction with one or two equivalents of H 2 , respectively.