Lanthanide complexes, stability

Eu(III) complexes of quinolinecarboxylic acids, including 5, were studied (00MI31). Those of complexes of 5 with Eu(III) and Tb(III) ion were studied, and they were applied for analysis of 5 in medicinal preparations (00UKZ115). Stability of lanthanide complexes with 5 was studied (00MI67). The fluorescence spectra of 5 complexed with Co(II) and ATP was measured (01SA(A)1317). 

In contrast to the situation observed in the trivalent lanthanide and actinide sulfates, the enthalpies and entropies of complexation for the 1 1 complexes are not constant across this series of tetravalent actinide sulfates. In order to compare these results, the thermodynamic parameters for the reaction between the tetravalent actinide ions and HSOIJ were corrected for the ionization of HSOi as was done above in the discussion of the trivalent complexes. The corrected results are tabulated in Table V. The enthalpies are found to vary from +9.8 to+41.7 kj/m and the entropies from +101 to +213 J/m°K. Both the enthalpy and entropy increase from ll1 "1" to Pu1 with the ThSOfj parameters being similar to those of NpS0 +. Complex stability is derived from a very favorable entropy contribution implying (not surprisingly) that these complexes are inner sphere in nature. 

As a result of their low redox potentials [173], bis(phthalocyaninato) lanthanide complexes are often inadvertently reduced or oxidized, and they are also very sensitive to acids and bases. In order to solve these problems, Veciana et al. achieved certain success on designing a series of novel compounds with characteristics that would give them improved redox stability. Electroactive ligands based on phthalo-cyaninato tetra dicarboximide [175] or perfluorinated phthalocyanine [176] were used to assemble the double-decker lanthanide complexes, with the effect of stabilizing the negative charge of the anionic state of the compounds, which resulted in a strong shift of 0.7 V of their first oxidation potentials. 

The trend toward greater complex stability with increasing lanthanide atomic number (see Table 3 for EDTA, DCTA, and DTPA complexes) has also been demonstrated for lanthanide complexes with... 

The stability constants for EDTA and DCTA undergo an increase in stability with increasing atomic number - a similar phenomenon has been observed for the lanthanide complexes (29). With DTPA, however, the stability constants undergo only a slight variation from Am(III) to Fm(III) such a phenomenon is also a characteristic of the equivalent lanthanide complexes. 

As the size of the chelating ligand increases, a maximum in stability is normally obtained for 5 or 6 membered rings. For lanthanide complexes, oxalate forms a 5-membered ring and is more stable than the malonate complexes with 6-membered rings. In turn, the latter are more stable than the 7-membered chelate rings formed by succinate anions. 

The Lu—C cr-bonding distances range from 2.425(15) to 2.501(17) A. These distances are approximately 0.2 A shorter than the corresponding distance for a pentahapto cyclopentadienide lutetium bond as predicted from ionic radii. Coordination about the lutetium atom is a slightly distorted tetrahedron. The formal coordination number of four is extremely low for the lanthanides. The only other lanthanide complex with such a low coordination number is the 3-coordinate compound [Lu N(SiMes)2 3] 131). In both cases, the low coordination number is stabilized by the use of bulky hgands. 

Complexes of calixarenes with bipyridyl chromophores can be stabilized by the addition of anionic side arms, such as iminodiacetate units (85). Whilst the lanthanide complexes of ligands [L51]4- and [L52]4- are not soluble in water, their photophysical properties in... 

Svetlitski, R., Lomaka, A., Karelson, M. 2006. QSPR modeling of lanthanide-organic complex stability constants. Sep. Sci. Technol. 41 (1) 197-216. 

Stability Constants (log P aN, ) of Lanthanide Complexes with OOCMPO and CPw2, CPw3, CPw17, and CPn3 in MeOH (/ = 0.05 M) Determined by UV Spectrophotometry... 

Hydrocarbonyl compounds, lanthanide complexes, 4, 4 ( -Hydrocarbyl)bis(zirconocene), preparation, 4, 906 Hydrocarbyl-bridged cyclopentadienyl-amido complexes, with Zr(IV), 4, 864 Hydrocarbyl complexes bis-Cp Ti hydrocarbyls reactions, 4, 551 structure and properties, 4, 551 synthesis, 4, 542 cobalt with rf-ligands, 7, 51 cobalt with rf-ligands, 7, 56 cobalt with ]4-ligands, 7, 59 cobalt with rf-ligands, 7, 71 heteroleptic types, 4, 192 homoleptic types, 4, 192 into magnetic metal nanoparticles via ligand stabilization, 12, 87 via polymer stabilization, 12, 87 into noble metal nanoparticles... 

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