Nine Ln( Ⅲ ) complexes with a novel Schiff base derived from diglycolamine and benzoylacetone (BZDA) have been synthesized and characterized. They can be formulated as [Ln2(BZDA)3(NO3)3](NO3)3· nH2O(Ln=La, Pr, Nd, Sm, n = 4; Ln=Gd, Tb, Er, Yb, Y, n = l). Enamic form mechanism in this β-diketone Schiff base and its complexes were suggested and proved by IR, UV and NMR methods. The 13C spin-lattice relaxation time T1 and the ratios of r(ci-Ln)/r(cj-Ln) were measured by a 500 MHz NMR instrument for elucidating the formation of the stable sk-membered chelate ring structure in these complexes. The EPR spectrum of the Gd( Ⅲ ) complex exhibits the 'U' spectral feature and 'zero field effect'. On the basis of them, the crystal field strength and the local symmetry around Gd3+ in the complex have been discussed.
A novel Schiff base (TAMET) was synthesized by the condensation of tetraglycol aldehyde with methionine and a mild oxidant CrO3. (C5H5N)2 was selected for the reaction. Seven new rare earth complexes with this Schiff base have been synthesized and characterized by elemental analysis, TG-DTA, molar Conductivity, magnetic susceptibility and IR, especially 1H NMR spectra. Information was obtained from reflectance spectra and the coordination of sulfur atom to rare earths was discussed. The experimental results show that these compounds have some biological activity and could dispose of O2?-.
A series of novel heteronuclear Ln( Ⅲ)-Cu( Ⅱ) complexes with noncyclic polyether-amino acid Schiff base were synthesized. The general formula is [LnCu2H2TALY)(NO3)5](NO3)2·nH2O (Ln= La, Nd, Sm, Gd, n = 4;Ln= Yb, Y, n = 3), where H2TALY = tetraglycol aldehyde bis-lysine Schiff base. It is the first time to report the synthetic method for this new Cu(Ⅱ) complexes and Ln( Ⅲ)-Cu( Ⅱ) heteronuclear complexes. The complexes were characterized by elemental analysis, IR spectra, TG-DTA, magnetic susceptibility, and especially by a 500 MHz NMR spectrometer for 2D-COSY NMR. Coordination mechanism and structures of complexes have been suggested as well. Of particular interest is the potential that the novel complexes obtained may be used as a catalyst, which prompted us to investigate them. It shows 100% conversion with the viscosity-average molecular weight 120 000 for the polymerization of methyl methacrylate (MMA) without addition of any cocatalyst. Furthermore, the complexes with such aliphatic Schiff bases can be used as a good catalyst, which has been confirmed and discussed here. They may be a new kind of catalyst system with the above speciality.
