Despite its generally poor catalytic properties, bulk gold metal is observed to catalyze reactions of isocyanides (CN-R) with primary amines (H2N-R') and O2 to give carbodiimides (R-N=C=N-R') at room temperature and above. Detailed infrared reflection absorption spectroscopic (IRRAS) and kinetic studies show that the reaction occurs by initial eta1-adsorption of the isocyanide on the Au surface, which activates the isocyanide to attack by the amine. This attack is the rate-determining step in the catalytic cycle and has characteristics very similar to those of amine reactions with coordinated isocyanides in transition metal complexes. However, the metallic Au surface provides a pathway involving O2 to give the carbodiimide product whereas homogeneous metal ion catalysts give formamidines [HC(=NR)(NHR')].
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