Stereoselective synthesis of biphenolate/binaphtolate titanate and zirconate alkoxide species: structural characterization and use in the controlled ROP of lactide.

Well-defined biphenol/binaphtolate group 4 alkoxide salt species [(Ph-Biphen-O)(2)M(O(i)Pr)]Li(THF) (2a, M = Ti; 4a, M = Zr) and [(Ph-binapht-O)(2)M(O(i)Pr)]Li(THF) (2b, M = Ti; 4b, M = Zr) were found to be readily accessible in good yields via alcohol elimination routes and/or substitution reactions from the corresponding pro-ligands Ph-Biphen-OH (1a) and rac-Ph-Binapht-OH (1b). As established via X-ray crystallographic analysis, the molecular structures of the Ti derivatives 2a and 2b consist of Li(+) salts of anionic Ti-O(i)Pr moieties in which the Ti center adopts a distorted tbp geometry and is effectively chelated by two biphenolate/binaphtolate units. Remarkably, the solution and solid state data for salt species 2a,b agree with the sole presence of one diastereomer (with a (Δ, aS, aS)/(Λ, aR, aR) configuration), thus indicating that formation of the Ti and Zr alkoxide complexes 2a,b/4a,b proceeds stereoselectively. In contrast, the neutral biphenolate/binaphtolate Zr complexes (Ph-biphen-O)(2)Zr(THF)(2) (3a) and (Ph-binapht-O)(2)Zr(THF)(2) (3b) were both isolated and X-ray characterized as stereomers in a heterochiral configuration (Δ, aR, aS)/(Λ, aS, aR). The Ti and Zr alkoxide anionic chelates were found to initiate the ROP of rac-lactide in a controlled manner for production of narrowly disperse and ester-end group PLA, as deduced from SEC, kinetic, and MALDI-TOF data. The Zr-O(i)Pr derivatives 4a,b exhibit superior performance to their Ti counterparts (whether regarding activity, polymerization control, or stereoselectivity) to produce narrowly disperse and heterotactically enriched PLA (P(r) = 0.67, PDI < 1.15). The significantly decreased Lewis acidity of the Zr metal center in anions 4a,b (versus neutral analogues) due to the anionic charge and a likely substantial electronic π donation of the four Zr-O(ArO) oxygens to the Zr metal center may rationalize the moderate polymerization activity. Control experiments suggest that the nature of the countercation has little influence on lactide ROP activity and stereocontrol.