The reaction of the dialkylzinc reagents R2Zn with the acids 2,2-Ph2C(X)(CO2H), where X ¼ NH2, OH, i.e. 2,20-diphenylglycine (dpgH) or benzilic acid (benzH2), in toluene at reflux temperature afforded the tetranuclear ring complexes [RZn(dpg)]4, where R ¼ Me (1), Et (2), 2-CF3C6H4 (3), and 2,4,6-F3C6H2 (4); complex 2 has been previously reported. The crystal structures of 1$(2MeCN), 3 and 4$(4(C7H8)$ 1.59(H2O)) are reported, along with that of the intermediate compound (2-CF3C6H4)3B$MeCN and the known compound [ZnCl2(NCMe)2]. Complexes 1–4, together with the known complex [(ZnEt)3(ZnL)3(benz)3] (5; L ¼ MeCN), have been screened, in the absence of benzyl alcohol, for their potential to act as catalysts for the ring opening polymerization (ROP) of 3-caprolactone (3-CL), dvalerolactone (d-VL) and rac-lactide (rac-LA); the co-polymerization of 3-CL with rac-LA was also studied. Complexes 3 and 4 bearing fluorinated aryls at zinc were found to afford the highest activities.