Catalytic Hydration of Benzonitrile and Acetonitrile using Nickel(0)

The homogeneous catalytic hydration of benzo‐ and acetonitrile under thermal conditions was achieved using nickel(0) compounds of the type [(dippe)Ni(η 2 ‐NCR)] with R=phenyl or methyl (compounds 1 and 2 , respectively), as the specific starting intermediates. Alternatively, the complexes may be prepared in situ by direct reaction of the precursor [(dippe)NiH] 2 ( 3 ) with the respective nitrile. Hydration appears to occur homogeneously, as tested by mercury drop experiments, producing benzamide and acetamide, respectively. Addition of Bu 4 NI did not lead to catalysis inhibition, suggesting the prevalence of Ni(0) intermediates during catalysis. Hydration using analogous complexes of 3 , such as [(dtbpe)NiH] 2 ( 4 ) and [(dcype)NiH] 2 ( 5 ) was also addressed.