Mechanistic studies of the copolymerization reaction of aziridines and carbon monoxide to produce poly-β-peptoids

The coupling of carbon monoxide and aziridines has been shown to be selective for comonomer-alternating enchainment in the presence of PhCH2C(O)Co(CO)(4) to afford poly-beta-peptoids. In this article, we have investigated the mechanistic aspects of the reaction of CO and N-butylaziridine by means of in situ infrared spectroscopy employing CH3C(O)CO(CO)(3)L (L = PPh3 (1) and P(o-tolyl)(3) (2)) as precatalysts. Precatalyst 1 exists in solution under catalytic conditions as an equilibrium mixture of 1 and CH3C(O)CO(CO)4, and affords both poly-beta-butylalanoid and the corresponding lactam. By way of contrast, precatalyst 2 which possesses the sterically bulky and labile P(o-tolyl)(3) ligand, affords only the acyl cobalt tetracarbonyl species in solution during catalysis with concomitant selective production of the copolymer. Kinetic studies conducted with precatalyst 2 showed the coupling reaction to have a first order dependence on catalyst, a first order dependence on N-butylaziridine, and only a slight dependence on the concentration of CO over the pressure range 17-69 bar. The working mechanistic model for the copolymerization reaction involves first aziridine insertion into the cobalt-acyl bond, rate determining ring opening by the cobaltate species, followed by the migratory CO insertion.