Homogeneous Catalytic Cleavage of Saturated Carbon‐Nitrogen Bonds

Abstract

AbstractAn evaluation of the catalytic reactivity of [CPD (CO)2RuH]2 (1) and (CPD)(CO)3Ru (2) (where CPD = tetraphenylcyclopentadienone) with amines suggests that these complexes catalyze C‐N bond cleavage by activating C‐H bonds alpha to the nitrogen atom of tertiary, secondary and primary amines at ca. 140° C. When two different amines are used, transalkylation takes place. With secondary and primary amines, ammonia and tertiary amines are formed. A series of amine complexes (CPD)(CO)2Ru.NR3 (R = alkyl/H) was isolated from stoichiometric reactions of 1 or 2 with primary and secondary amines. It was found that tertiary amines do not generate complexes of the above type but rather unexpectedly give secondary amine complexes by cleavage of an alkyl group. The only isolatable tertiary amine complex is the moderately stable (CPD)(CO)2RuNMe3. All amine complexes were characterized by spectral and elemental analyses. Catalytic aspects of C‐N bond cleavage were studied. Complexes (1) and (2) were found to react with primary, secondary and tertiary amines to generate imminium or eneamine species which subsequently undergo hydrolysis with water. This is in contrast to the Ru carbene mechanism previously proposed for cluster catalyzed C‐N bond activation and cleavage. The two reactions are compared with respect to D for H exchange (with D2O), water requirement and production of trace products during catalysis. A primary alcohol was found to substitute alkyl groups of a tertiary amine under the catalytic action of 1. A catalytic reaction cycle is proposed.