Selective Hydrogenation of Amides to Amines and Alcohols Catalyzed by Improved Iron Pincer Complexes

A comparative study on the synthesis, stability, and catalytic activity of various iron pincer complexes with the general formula [(R-PN H P)Fe(H) (CO) (BH 4 )] is reported, where R denotes the substituent of the terminal PR 2 -groups (R = t Bu, Cy, i Pr, Ph, Et). By the example of the synthesized precatalysts, it is shown that the nature of the ligands has a surprising influence on the catalytic properties of the complexes. Bulky ligands and less electron donating ligands affect the stability of the complexes, which preferably react under the loss of CO or H 2 to deactivated products. In return, the reduced steric demand and the strong σ-donating properties of the Et-substituted precatalyst ( 2a ) lead to an improved activity in the hydrogenation of esters to alcohols, compared to that of the previously reported i Pr-substituted complexes. The improved activity of complex 2a is clearly demonstrated in the direct hydrogenation of amides to alcohols and amines under mild conditions.