Synthesis and characterization of guanidinate tin(ii) complexes for ring-opening polymerization of cyclic esters.

Novel homoleptic and heteroleptic (guanidinate)tin(ii) complexes were successfully synthesized and structurally characterized. The first heteroleptic (guanidinato)tin(ii) alkoxide complex was synthesized but found to be unstable leading to the corresponding bis(guanidinate)tin(ii) complex. The catalytic activities of bis(guanidinate)tin(ii) complexes having different substituents at the nitrogen atoms (isopropyl (1), cyclohexyl (2), and p-tolyl (3)) were investigated in the ring-opening polymerization (ROP) of ε-caprolactone (ε-CL) and lactide (LA). The lone-pair electrons of the tin(ii) atom were proposed to act as an initiator similar to N-heterocyclic carbenes. Among the synthesized catalysts, complex 1 having less steric hindrance efficiently catalyzed both homo- and copolymerizations of ε-CL and LA giving high molecular weight cyclic polyesters. Transesterification was found to be the major contributor to the cyclization to cyclic polyesters.

Hierarchical FAU/ZIF-8 Hybrid Materials as Highly Efficient Acid-Base Catalysts for Aldol Condensation.

The composite of hierarchical faujasite nanosheets and zeolitic imidazolate framework-8 (Hie-FAU-ZIF-8) has been successfully prepared via a stepwise deposition of ZIF-8 on modified zeolite surfaces. Compared to the direct deposition of metal organic frameworks (MOFs) on zeolite surfaces, ZIF-8 nanospheres were selectively attached to the external surfaces of the MOF ligand-grafted FAU crystals because of the enhancing interaction between the zeolite and MOF in the composite. In addition, the degree of surface functionalization can be greatly enhanced because of the presence of hierarchical structures. This behavior leads to an increase in the deposited MOF content, improving the hydrophobic properties of the zeolite surfaces. Interestingly, the designed hierarchical composite exhibits outstanding catalytic properties as an acid-base catalyst for the aldol condensation of 5-hydroxymethylfurfural with acetone. Compared to the isolated FAU and ZIF-8, a high yield of the product, 4-[5-(hydroxymethyl)furan-2-yl]but-3-en-2-one (67%), can be observed in the composite because of the synergistic effect between the Na+-stabilized zeolite framework and the imidazolate linkers bearing basic nitrogen functions. This opens up interesting perspectives for the development of new organic and inorganic hybrid materials as heterogeneous acid-base catalysts.