The isomerization of N-allylamines ((RRNCH2CH)-R-1-N-2=CH2 and PhMeNCH2CH=CHSiMe3) catalyzed by [RhH(CO)(PPh3)(3)] or [RuCIH(CO)(PPh3)(3)] to corresponding I-propenyl derivatives is described. In the case of the ruthenium complex, double bond migration was successful only in the case of allylamines with bulky groups (Me3C, Me3Si, Me2CH) at the nitrogen atom. A strong E-selectivity in the isomerization of allylamines was observed. It is postulated that the E-selectivity of double bond migration is the result of a specific coordination of the metal atom by the phenyl substituent or the nitrogen atom. This hypothesis has been confirmed by theoretical calculations tab initio) performed for some N-allylamines and enamines. (c) 2005 Elsevier B.V. All rights reserved.