Chiral Rare Earth Borohydride Complexes Supported by Amidinate Ligands: Synthesis, Structure, and Catalytic Activity in the Ring-Opening Polymerization of rac-Lactide

The monoamidinato bisborohydride rare earth complexes [Ln{(S)-PEBA}(BH4)(2)(THF)(2)] (Ln = Sc (1), La (2), Nd (3), Sm (4), Yb (5), Lu (6)) were isolated as crystalline materials upon treatment of potassium N,N'-bis((S)-1-phenylethyl)benzamidinate ((S)-KPEBA) with the homoleptic trisborohydrides [Sc(BH4)(3)(THF)(2)] and [Ln(BH4)(3)(THF)(3)] (Ln = La, Nd, Sm, Yb, Lu), respectively. Compounds 1-6 are unique examples of enantiopure borohydride complexes of the rare earth metals. Different ionic radii of the metal centers were selected to cover the whole range of these elements with respect to the extent of the coordination sphere. All new complexes were thoroughly characterized by H-1, C-13{H-1}, B-11, and N-15 NMR and IR spectroscopies, also including single-crystal X-ray diffraction structure determination of each compound. The scandium, lanthanum, samarium, and lutetium complexes 1, 2, 4, and 6 were found active in the ring-opening polymerization of rac-lactide under mild operating conditions, providing atactic alpha,omega-dihydroxytelechelic poly(lactic add) (PLA; M-n,M-SEC up to 18 800 g.mol(-1)). Most of the polymerizations proceed with a certain degree of control that is directed by molar mass values and relatively narrow dispersities (1.10 < D-M < 1.34), within a moderate monomer-to-initiator ratio.