Two monomeric, six-coordinated magnesium complexes with bulky aminophenolate ligands [(Htbpoa)2Mg] (1) and [(Htbpca)2Mg(THF)2] (2), where Htbpoa =N-[methyl(2-hydroxy-3,5-di-tert-butylphenyl)]-N-methyl-N-methyl-1,3-dioxolaneamine and Htbpca =N-[methyl(2-hydroxy-3,5-di-tert-butylphenyl)]-N-methyl-N-cyclohexylamine have been prepared, characterized and employed as initiators for lactide polymerization. The crystal structure of the homoleptic compound 1 has been determined and shows that the six-coordinate magnesium atom in 1 is surrounded by two tridendate tbpoa ligands. In the solution, however, complex 1 exists in equilibrium with a five-coordinate species 1a having one oxolane fragment dangling. The tbpoa and tbpca ligands in 1 and 2 play a dual role, as the ancillary ligand stabilizing the monomeric magnesium species and as the initiating polymerization group.
A cluster of lanthanide(III) or yttrium(III) ions, Ln3(μ3-OH)2, (Ln(III) = Nd(III), Sm(III), Eu(III), Gd(III), Tb(III), Dy(III), Yb(III), or Y(III)) can be bound in the center of a chiral macrocyclic amines H3L1(R), H3L1(S), and H3L2(S) obtained in a reduction of a 3 + 3 condensation product of (1R,2R)- or (1S,2S)-1,2-diaminocyclohexane and 2,6-diformyl-4-methylphenol or 2,6-diformyl-4-tertbutylphenol. X-ray crystal structures of the Nd(III), Sm(III), Gd(III), Dy(III), and Y(III) complexes reveal trinuclear complexes with Ln(III) ions bridged by the phenolate oxygen atoms of the macrocycle as well as by μ3-hydroxo bridges. In the case of the Nd(III) ion, another complex form can be obtained, whose X-ray crystal structure reveals two trinuclear macrocyclic units additionally bridged by hydroxide anions, corresponding to a [Ln3(μ3-OH)]2(μ2-OH)2 cluster encapsulated by two macrocycles. The formation of trinuclear complexes is confirmed additionally by (1)H NMR, electrospray ionization mass spectrometry (ESI MS), and elemental analyses. Titrations of free macrocycles with Sm(III) or Y(III) salts and KOH also indicate that a trinuclear complex is formed in solution. On the other hand, analogous titrations with La(III) salt indicate that this kind of complex is not formed even with the excess of La(III) salt. The magnetic data for the trinuclear Gd(III) indicate weak antiferromagnetic coupling (J = -0.17 cm(-1)) between the Gd(III) ions. For the trinuclear Dy(III) and Tb(III) complexes the χ(M)T vs T plots indicate a more complicated dependence, resulting from the combination of thermal depopulation of mJ sublevels, magnetic anisotropy, and possibly weak antiferromagnetic and ferromagnetic interactions.
The contents and composition of essential oils obtained from Heracleum sosnowskyi and Heracleum mantegazzianum (Apiaceae) were examined. essential oils were investigated by the GC/MS method. The composition of hogweeds’ essential oils was examined in order to determine toxic compounds that could have a direct influence on the health of people and animals living in close proximity to both species. It was found that the essential oils, except for derivatives of coumarins, contain numerous toxic compounds, e.g. isobutyl isobutyrate, isoamyl butyrate, hexyl hexanoate, 1-hexadecanol etc. No significant differences were found in the chemical composition of the examined seed samples of Heracleum, which confirms the suggestions that the species can be closely related
Depending on the reaction conditions, the enantiopure macrocycle H3L containing three phenolic units is able to form mono‐ and trinuclear coordination compounds with rare earth metal ions. In these complexes this macrocycle can act as protonated H4L+, neutral H3L, monodeprotonated H2L–, bis‐deprotonated HL2– or tris‐deprotonated L3– ligand. X‐ray crystal structure of the Y(III) derivative of the protonated macrocycle shows highly folded conformation of the ligand with N2O3 set of donor atoms, while the structure of the Y(III) complex of the monodeprotonated macrocycle shows more regular helically twisted conformation of the ligand. Under basic conditions trinuclear complexes of the type [M3L(OH)2] are formed with most of rare earth ions, where the macrocycle acts as N6O3 ligand. This type of complex is not formed for the La(III) and Ce(III) ions of the largest radii within the lanthanide(III) series, instead trinuclear complexes of the type [M3L2] are formed. The X‐ray crystal structures of La(III) complex with fully deprotonated or bis‐deprotonated macrocycles indicate that each macrocyclic unit binds only two metal ions, while one of them is shared by two macrocycles.
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