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The synthesis and characterization of (thiolfan*)Zr(OtBu)2 (thiolfan* = 1,1′-di(2,4-di-tert-butyl-6-thiophenoxide)ferrocene) is reported, as well as its activity toward the ring-opening polymerizations of L-lactide and e-caprolactone. With the titanium analogue, (thiolfan*)Ti(OiPr)2, diblock copolymers (AB and BA) and a triblock copolymer (ABA) were synthesized in a one-pot, redox-controlled process. Changing the metal center from titanium to zirconium has a profound influence on the reactivity profile of the corresponding reduced and oxidized catalysts in the switchable ring opening polymerization of cyclic esters and ethers.

Investigation of redox switchable titanium and zirconium catalysts for the ring opening polymerization of cyclic esters and epoxides