Heterobimetallic rare earth metal-zinc catalysts for reactions of epoxides and CO2 under ambient conditions.

Four homodinuclear rare earth metal (RE) complexes 1-4 bearing a multidentate diglycolamine-bridged bis(phenolate) ligand were synthesized. In addition, seven heterobimetallic RE-Zn complexes 5-11 were prepared through a one-pot strategy. In these heterobimetallic complexes, two RE centers are bridged by either Zn(OAc)2 or Zn(OBn)2 moieties. All complexes were characterized by single crystal X-ray diffraction, elemental analysis, IR spectroscopy, and multinuclear NMR spectroscopy (in the case of diamagnetic complexes 1, 4, 7 and 11). Moreover, the multi-nuclear structures of complexes 4 and 11 in solution were also studied by 1H DOSY spectroscopy. These complexes were applied in catalyzing the coupling reaction of carbon dioxide (CO2) with epoxides. Zn(OAc)2- and Zn(OBn)2-bridged heterobimetallic complexes showed comparable catalytic activities under ambient conditions and were more active than monometallic RE complexes. Significant synergistic effect in heterobimetallic complexes is observed. Mono-substituted epoxides were converted into cyclic carbonates under 1 atm CO2 at 25 °C in 88-96% yields, whereas di-substituted epoxides reacted under 1 atm CO2 at higher temperatures in 40-80% yields.

Synthesis of Homo- and Heteronuclear Rare-Earth Metal Complexes Stabilized by Ethanolamine-Bridged Bis(phenolato) Ligands and Their Application in Catalyzing Reactions of CO2 and Epoxides.

A series of homonuclear rare-earth (RE) metal complexes (1Y, 2Yb, 3Nd, and 4La) and heteronuclear RE-Zn complexes (1Y-Zn, 3Nd-Zn, and 5Sm-Zn) stabilized by ethanolamine-bridged bis(phenolato) ligands was prepared and structurally characterized. Heteronuclear complexes are assembled through bridging acetate ligands, and their formation and characterization add to the diversity of 3d-4f complexes. Their activities in mediating reactions of CO2 and epoxides were evaluated and compared. Heteronuclear RE-Zn complexes found application in the copolymerization of cyclohexene oxide and CO2, giving rise to acetate-group-capped copolymers. Homonuclear complexes showed good activity in catalyzing the cycloaddition of variously monosubstituted epoxides and CO2 (1 bar), generating cyclic carbonates in 65-96% yield. For sterically hindered disubstituted epoxides, good yields of 60-91% were achieved in the presence of 10 bar CO2.

Rare-earth/zinc heterometallic complexes containing both alkoxy-amino-bis(phenolato) and chiral salen ligands: synthesis and catalytic application for copolymerization of CO2 with cyclohexene oxide.

Ten rare-earth/zinc heterometallic complexes containing both alkoxy-amino-bis(phenolato) and chiral salen ligands were synthesized from the reactions of alkoxy-amino-bis(phenolato) rare-earth complexes with chiral salen zinc complexes via ligand redistribution and THF disassociation. Six of them were characterized by single-crystal X-ray diffraction, which showed 6-coordinate rare-earth and 5-coordinate zinc centres in the complexes. A primary catalytic application of these heterometallic complexes was studied, and it was found that samarium/zinc and dysprosium/zinc heterometallic complexes are highly efficient catalysts for copolymerization of CO2 with cyclohexene oxide while the alkoxy-amino-bis(phenolato) samarium complex and chiral salen zinc complex show very low catalytic activity or no catalytic activity for this copolymerization.