The role of phosphine in cobalt-catalyzed carbonylative polymerization of N-alkylaziridine
摘要:
A series of CH3COCo(CO)(3)L complexes (1, L = PCy3; 2, L = PMe2Ph; 3, L = PPh3; 4, L = P(para-F-Ph)(3); 5, L = P(meta-F-Ph)(3); and 6, L = P(ortho-tolyl)(3)) were studied as precatalyst for the title polymerization. The Co-P bond length primarily responds to the cone angle of the phosphine ligand (6 > 1 > 2 approximate to 3 approximate to 4 approximate to 5), while the back-donation to the axial acetyl ligand and the equatorial CO ligand depends on the electron-donating ability of the phosphine and increases in the order 1 > 6 > 2 > 3 > 4 > 5. The equilibrium constant for CH3COCo(CO)(3)L + CO <-> CH3COCO(CO)(4) + L depends on the electron-donating ability of the phosphine ligand except for 6 and follows the order 6 >> 5 > 4 > 3 > 2 > 1. The catalytic activity follows the order 6 > 5 > 4 > 3 > 1 > 2. The activity difference cannot be explained solely by the above equilibrium and is consistent with the competition for the acyl site by the phosphine as nucleophile against aziridine. The production of the beta-lactam byproduct is attributed to catalyst decomposition, which is accelerated to the basicity/nucleophilicity of the phosphine ligand. (c) 2005 Elsevier B.V. All rights reserved.