Bifunctional Water Activation for Catalytic Hydration of Organonitriles

Treatment of [Rh­(COD)­(μ-Cl)]₂ with excess ^<i>t</i>BuOK and subsequent addition of 2 equiv of PIN·HBr in THF afforded [Rh­(COD)­(κC₂-PIN)­Br] (<b>1</b>) (PIN = 1-isopropyl-3-(5,7-dimethyl-1,8-naphthyrid-2-yl)­imidazol-2-ylidene, COD = 1,5-cyclooctadiene). The X-ray structure of <b>1</b> confirms ligand coordination to “Rh­(COD)­Br” through the carbene carbon featuring an unbound naphthyridine. Compound <b>1</b> is shown to be an excellent catalyst for the hydration of a wide variety of organonitriles at ambient temperature, providing the corresponding organoamides. In general, smaller substrates gave higher yields compared with sterically bulky nitriles. A turnover frequency of 20 000 h^–1 was achieved for the acrylonitrile. A similar Rh­(I) catalyst without the naphthyridine appendage turned out to be inactive. DFT studies are undertaken to gain insight on the hydration mechanism. A 1:1 catalyst–water adduct was identified, which indicates that the naphthyridine group steers the catalytically relevant water molecule to the active metal site via double hydrogen-bonding interactions, providing significant entropic advantage to the hydration process. The calculated transition state (TS) reveals multicomponent cooperativity involving proton movement from the water to the naphthyridine nitrogen and a complementary interaction between the hydroxide and the nitrile carbon. Bifunctional water activation and cooperative proton migration are recognized as the key steps in the catalytic cycle