A series of lithium, sodium, and
potassium complexes with phenoxo-imine
ligands M[(O-2-(RNCH)C6H4] [R = C6H5; 2-
t
BuC6H5; 2,6-
i
Pr2C6H3] and [O-2-(RNCH)-4,6-
t
Bu2C6H4] [R = C6H5; 2-
t
BuC6H5; 2,6-
i
Pr2C6H3] 1–3(a–f) have been synthesized. The molecular structures
in the solid state of some of these complexes have been determined
by X-ray diffraction. These compounds show different nuclearities
and geometries around the metal center depending on the nature and
the pocket of the ligand substituents. Of particular interest is the
structure of compound 3e, being the first example of
a potassium cubane complex obtained with this kind of ligand. The
structural behavior in solution has also been studied by diffusion-ordered
NMR spectroscopy (DOSY), showing a direct correlation between aggregation
behavior and polymerization activity. Compounds 1–3(a–f) are extremely active
catalysts in the ring-opening polymerization (ROP) of rac-lactide, achieving conversions of 100% in less than 1 min and heterorich-PLA
that is modified by the metal atom and the ligand substituents. BnOH
was used as co-initiator, and the presence of large amounts of the
alcohol produces the immortal polymerization of rac-lactide in a more controlled process. Stoichiometric reactions involving
the catalysts, BnOH, and lactide demonstrated an activated monomer
mechanism for the polymerization of rac-lactide.
A Zn-based metal-organic framework (MOF) with hydrazinebenzoate linkers was evaluated as antimicrobial material against the Gram-positive bacterium Staphylococcus aureus. The material inhibits bacterial growth and metabolic activity, with a half maximal effective concentration of about 20 mg L -1 [a
Reduction of phenol-imine derivatives RЈN=CH(3,5-R 2 C 6 H 2 -2-OH) (R = tBu; RЈ = C 6 H 5 1a, p-MeC 6 H 4 1b, Cy 1c, tBu 1d, 2,6-Me 2 C 6 H 3 1e; R = H; RЈ = p-MeC 6 H 4 1f; Cy = cyclohexyl) with MBH 4 (M = Li, Na) or AlLiH 4 in ethyl ether or thf at room temperature affords the phenol-amine compounds RЈNHCH 2 (3,5-R 2 C 6 H 2 -2-OH) 2a-c and 2e,f. The N-R- [2,4-ditert-butyl]benzo-1-oxa-3-azine species (R = tBu 2d1, 2,6-Me 2 C 6 H 3 2e1) are obtained by Mannich reaction of 2,4-ditert-butylphenol with RNH 2 in refluxing methanol. Intermediate 2d1 is converted in ethanol at room temperature into N-tert-butyl [2-hydroxy-3,5-di-tert-butyl]benzylamine (2d), whereas 2e is not obtained from 2e1 by using this procedure.
N-alkyl,N-tert-butyl[2-hydroxy-3,5-di-tert-butyl]benzylamine compounds tBuN(R)CH
Crystal size 0.35 x 0.20 x 0.19 mm Theta range for data collection 3.33 to 27.51 deg. Limiting indices -18<=h<=18, -12<=k<=12, -14<=l<=14 Reflections collected / unique 34587 / 3713 [R(int) = 0.0509] Completeness to theta = 27.51 99.6 % Absorption correction Semi-empirical from equivalents Max. and min. transmission 0.785 and 0.597 Refinement method Full-matrix least-squares on F^2
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