Diverse mechanistic pathways and selectivities in organo-f-element-catalyzed hydroamination. Intermolecular organolanthanide-catalyzed alkyne and alkene hydroamination

Lanthanide metallocenes catalyze the regiospecific intermolecular addition of primary amines to acetylenic, olefinic, and diene substrates at rates which are similar to 1/1000 those of the most rapid intramolecular analogues. Kinetic and mechanistic data argue for turnover-limiting C=C/C=C insertion into a Ln-N bond, followed by protonolysis of the resulting Ln-C bond.