Cobalt-Rhodium Heterobimetallic Nanoparticle Catalyzed Amination Using Hydrogen-Borrowing Strategy

Abstract

Part 1. Conversion of Primary Amines to Symmetrical Secondary and Tertiary Amines Using a Co-Rh Heterobimetallic Nanocatalyst Symmetrical tertiary amines have been efficiently realized from amine and secondary amines via deaminated homocoupling with heterogeneous bimetallic Co2Rh2/C as catalyst (molar ratio Co:Rh= 2:2). Unsymmetric secondary anilines were produced from the reaction of anilines with symmetric tertiary amines. The Co2Rh2/C catalyst exhibited very high catalytic activity towards a wide range of amines and could be conveniently recycled ten times without considerable leaching.

Part 2. Cobalt-Rhodium Heterobimetallic Nanoparticle-Catalyzed Alkylation of Amines with Alcohols to Secondary and Tertiary Amines Co2Rh2/C without the need for base or other additives is able to selectively catalyze both dehydrogenative mono- and diamination (N-alkylation) through coupling of simple alcohols with amines effectively yielding a range of secondary and tertiary amines in good to excellent isolated yields. Selectivity is achieved by varying the reaction temperature and the amount of catalyst used.