RESUMEN
Using dialkylgallium alkoxides with N-hetrocyclic carbenes (Me2GaOR(NHC)) for the ring-opening polymerization of rac-lactide, we have demonstrated the effect of the chelate interaction between the growing PLA chain and gallium on the stereoselectivity of dialkylgallium alkoxide propagating species - Me2Ga(OPLA)(NHC). In order to do so, we have conducted the structure-activity studies of both Me2Ga(OCH2CH2OMe)(NHC) (NHC = SIMes (1) and IMes (2)) and Me2Ga(OCH(Me)CO2Me)(NHC) (NHC = SIMes (3) and IMes (4)), the latter mimicking active species in the ROP of lactide with growing PLA chain. Based on VT NMR and FTIR spectroscopy, the effect of toluene, CH2Cl2 and THF on the structure of 3 and 4 have been demonstrated, especially with regard to the interaction of methyl lactate ligand with gallium. In a combination with the latter, the studies on the activity of 1 and 2 in the ROP of rac-LA, in different solvents, and at temperatures between -40 °C and 40 °C, have shown the extent of the chelation effect on the isoselectivity of Me2Ga(OPLA)(NHC) in the ROP of rac-LA, which varied between P m of 0.75 and 0.89 depending on the polymerization conditions. Both the latter, and the contribution resulting from the structure of Me2Ga(OPLA)(NHC) (P m = 0.75) have been decisive for the total isoselectivity observed under specific conditions. Our finding represents the first evidence demonstrating that the chelation effect, resulting from the weak interaction between the growing PLA chain and the metal centre, can be responsible for the enhancement of stereoselectivity in the ROP of rac-LA with metal alkoxide propagating species. It should remain of interest, especially in the case of metal based catalysts, which are able to carry out the stereoselective polymerization of rac-LA at mild conditions, under which the chelation effect can manifest itself.
RESUMEN
While aluminum alkyls are often considered to be exemplary compounds of main-group organometallics and an in-depth understanding of their multifaceted chemistry is continually vital, the controlled oxygenation of organoaluminum complexes still remains a largely undeveloped area. In the course of our systematic studies on the relationship between the Lewis acidity of metal centers and noncovalent interactions in the secondary coordination sphere, we report the oxygenation of dialkylaluminum complexes incorporating a pyrrole-ester ligand, as purposefully selected dormant Lewis acidic octet-compliant model compounds, and the isolation and characterization of a new, dimeric aluminum tert-butylperoxide and an unique example of an aluminum oxoethoxide cluster. Our studies provide a more in-depth look at the diversity and complexity of the oxygenation chemistry of aluminum alkyls.
RESUMEN
An atom-efficient and mild synthesis of a series of oxozinc carboxylates [Zn(4)(µ(4)-O)(O(2)CR)(6)] [where R = Ph (2a), p-PhC(6)H(4) (2b), p-MeC(6)H(4) (2c), and p-MeSC(6)H(4) (2d)] from well-defined alkylzinc precursors and H(2)O is described. The molecular and crystal structures of the resulting complexes have been determined by single-crystal X-ray diffraction. A closer examination of their crystal structure provides a direct picture of the effect of the nature of substituents on the molecular self-assembly of the octahedral oxozinc through noncovalent interactions. It was revealed that these discrete oxozinc clusters can form diverse types of noncovalent assemblies ranging from structures representing zeolitic topologies in the case of 2a to soft porous materials with gated voids or open channels for the remaining molecular clusters.