Complexation of Lanthanides with Glutaroimide-dioxime: Binding Strength and Coordination Modes

Inorganic Chemistry
Seraj A AnsariLinfeng Rao

Abstract

The complexation of lanthanides (Nd(3+) and Eu(3+)) with glutaroimide-dioxime (H2L), a cyclic imide dioxime ligand that has been found to form stable complexes with actinides (UO2(2+) and NpO2(+)) and transition metal ions (Fe(3+), Cu(2+), etc.), was studied by potentiometry, absorption spectrophotometry, luminescence spectroscopy, and microcalorimetry. Lanthanides form three successive complexes, M(HL)(2+), M(HL)L, and M(HL)2(+) (where M stands for Nd(3+)/Eu(3+) and HL(-) stands for the singly deprotonated ligand). The enthalpies of complexation, determined by microcalorimetry, show that the formation of these complexes is exothermic. The stability constants of Ln(3+)/H2L complexes are several orders of magnitude lower than that of the corresponding Fe(3+)/H2L complexes but are comparable with that of UO2(2+)/H2L complexes. A structure of Eu(3+)/H2L complex, identified by single-crystal X-ray diffractometry, shows that the ligand coordinates to Eu(3+) in a tridentate mode, via the two oxygen atoms of the oxime group and the nitrogen atom of the imide group. The relocation of protons of the oxime groups (-CH═N-OH) from the oxygen to the nitrogen atom, and the deprotonation of the imide group (-CH-NH-CH-) result in a conjugated ...Continue Reading

References

Dec 25, 2007·Acta Crystallographica. Section A, Foundations of Crystallography·George M Sheldrick
Jul 18, 2012·Dalton Transactions : an International Journal of Inorganic Chemistry·Guoxin TianLinfeng Rao
Feb 28, 2013·Dalton Transactions : an International Journal of Inorganic Chemistry·Guoxin TianLinfeng Rao
Aug 30, 2013·Dalton Transactions : an International Journal of Inorganic Chemistry·Xiaoqi SunLinfeng Rao
Oct 16, 2013·Dalton Transactions : an International Journal of Inorganic Chemistry·Xiaoqi SunBenjamin P Hay

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Citations

Jun 14, 2016·Chemical Communications : Chem Comm·Zachary C KennedyMarvin G Warner
Jun 8, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Zhicheng ZhangLinfeng Rao

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