Carbodiimide Synthesis via Ti-Catalyzed Nitrene Transfer from Diazenes to Isocyanides

Simple Ti imido halide complexes such as [Br₂Ti(N^tBu)py₂]₂ are competent catalysts for the synthesis of unsymmetrical carbodiimides via Ti-catalyzed nitrene transfer from diazenes or azides to isocyanides. Both alkyl and aryl isocyanides are compatible with the reaction conditions, although product inhibition with sterically unencumbered substrates sometimes limits the yield when diazenes are employed as the oxidant. The reaction mechanism has been investigated both experimentally and computationally, wherein a key feature is that the product release is triggered by electron transfer from an η²-carbodiimide to a Ti-bound azobenzene. This ligand-to-ligand redox buffering obviates the need for high-energy formally Ti^II intermediates and provides further evidence that substrate and product "redox noninnocence" can promote unusual Ti redox catalytic transformations.