Bis(phosphinimino)methanide borohydride complexes of the rare-earth elements as initiators for the ring-opening polymerization of ε-caprolactone: combined experimental and computational investigations

Abstract

Rare-earth-metal borohydrides are known to be efficient catalysts for the polymerization of apolar and polar monomers. The bis-borohydrides [{CH(PPh2 NSiMe3)2}La(BH4)2(THF)] and [{CH(PPh2NSiMe3)2}Ln(BH4)2] (Ln = Y, Lu) have been synthesized by two different synthetic routes. The lanthanum and the lutetium complexes were prepared from [Ln(BH4)3(THF)3] and K{CH(PPh2NSiMe3)2}, whereas the yttrium analogue was obtained from in situ prepared [{CH(PPh2NSiMe3)2}YCl2]2 and NaBH4. All new compounds were characterized by standard analytical/spectroscopic techniques, and the solid-state structures were established by single-crystal X-ray diffraction. The ring-opening polymerization (ROP) of ε-caprolactone initiated by [{CH(PPh2NSiMe3)2}La(BH4)2(THF)] and [{CH(PPh2NSiMe3)2}Ln(BH4)2] (Ln = Y, Lu) was studied. At 0 °C the molar mass distributions determined were the narrowest values (M(w)/M(n) = 1.06-1.11) ever obtained for the ROP of ε-caprolactone initiated by rare-earth-metal borohydride species. DFT investigations of the reaction mechanism indicate that this type of complex reacts in an unprecedented manner with the first B-H activation being achieved within two steps. This particularity has been attributed to the metallic fragment based on the natural bond order analysis.

Keywords: boron; density functional calculations; lactones; rare earths; ring-opening polymerization.