Skip to main content
SpringerLink
Log in

Investigation of lanthanide complexation with acetohydroxamic acid in nitrate medium: experimental and DFT studies

  • Regular Article
  • Published:
Journal of Chemical Sciences Aims and scope Submit manuscript

A Correction to this article was published on 20 July 2021

This article has been updated

Abstract

Complexation study of acetohydroxamic (AHA) ligand with La(III), Nd(III), Eu(III), Er(III), and Lu(III), as representative of lanthanide (Ln) series, has been described, in presence of pure nitrate and combination of nitrate and perchlorate ions using various spectroscopic analysis and density functional theory (DFT) calculations. Nuclear magnetic resonance (NMR) spectroscopy reports the bidentate mode of coordination of Z-Keto tautomer of AHA monomer with La(III). Formation of 1:3 Nd(III)-AHA complexes in presence of pure nitrate and a combination of nitrate and perchlorate ions has been observed from ultraviolet-visible (UV-Vis) spectroscopy analysis. The geometrical parameter analysis exhibit the bidentate mode coordination fashion of the AHA monomer which corroborates the NMR results. The geometrical parameter, frontier orbital(HOMO-LUMO), global reactivity descriptors and local reactivity descriptors analysis supports the findings of the spectroscopy titration methods that stability of Ln-AHA complexes decreases in the presence of pure nitrate ions than in presence of both perchlorate and nitrate ions. The trend of theoretical NMR chemical shifts of AHA and La(III)-AHA complexes support the experimental NMR chemical shifts. This work helps to measure subtle differences in complexation behaviour of AHA with Ln in presence of pure nitrate and a combination of nitrate and perchlorate ions quantitatively, providing information about the Ln-AHA structural environment.

Graphic abstract

Various spectroscopic methods (UV-Vis, NMR, and Fluorescence spectroscopy) and density functional theory (DFT) calculations have been implemented for structural characterization of lanthanides (Ln(III))-acetohydroxamic acid(AHA) complexes in the presence of a combination of both perchlorate and nitrate ions and in pure nitrate ions. The Ln(III)-AHA complexes show more stability in the presence of a combination of both perchlorate and nitrate ions than in the presence of nitrate ions which is supported by DFT calculations.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Figure 1
Figure 2
Figure 3
Figure 4
Figure 5
Figure 6
Figure 7
Figure 8
Figure 9
Figure 10

Similar content being viewed by others

Change history

References

  1. Sanchez-Garcia I, Bonales L J, Galan H, Perlado J M and Cobos J 2019 Advanced direct method to quantify the kinetics of acetohydroxamic acid (AHA) by Raman spectroscopy Spectrochim. Acta Part A 117877

  2. Senent M L, Nino A, Caro C M, Ibeas S, Garcia B, Leal J M and Venturini M 2003 Deprotonation sites of acetohydroxamic acid isomers. A theoretical and experimental study J. Org. Chem. 68 6535

  3. Gupta S P 2013 Hydroxamic Acids: A Unique Family of Chemicals with Multiple Biological Activities (Berlin: Springer)

    Book  Google Scholar 

  4. Sastri V S, Bunzli J C, Rao V R, Rayudu G V S and Perumareddy J R 2003 Modern Aspects of Rare Earths and Their Complexes (Amsterdam: Elsevier B V)

    Google Scholar 

  5. Wu W, Sun T, Pu N, Meng D, Li Y, Dang J and Xu C 2018 Thermodynamic and spectroscopic study on the solvation and complexation behavior of Ln(III) in ionic liquids: binding of Ln(III) with CMPO in C4mimNTf2 New J. Chem. 42 9098

    CAS  Google Scholar 

  6. Fedorov Yu S, Zilberman B Ya and Poverkova L Ya 2000 Solvate forms of Np (4) in TBP during extraction from nitric acid solutions in the presence of uranyl nitrate Radiokhimiya 42 417

  7. Chung D, Choi E and Lee E 2011 Complexation of U (VI), Ce (III) and Nd (III) with acetohydroxamic acid in perchlorate aqueous solution J. Radioanal. Nucl. Chem. 289 315

    Article  CAS  Google Scholar 

  8. Sinkov S I, Choppin G R and Taylor R J 2007 Spectrophotometry and luminescence spectroscopy of acetohydroxamate complexes of trivalent lanthanide and actinide ions J. Solution Chem. 36 815

    Article  CAS  Google Scholar 

  9. Sinkov S and Choppin G 2002 Acetohydroxamic acid complexes with trivalent f-block metal cations J. Nucl. Sci. Technol. 39 359

    Article  Google Scholar 

  10. Choppin G R, Liljenzin J O and Rydberg J 2002 Radiochemistry and Nuclear Chemistry (Amsterdam: Reed Elsevier Group)

    Google Scholar 

  11. Pathak P N, Mohapatra M and Godbole S V 2013 Photoluminescence studies on the complexation of Eu (III) and Tb (III) with acetohydroxamic acid (AHA) in nitrate medium Spectrochim. Acta Part A 115 805

    Article  CAS  Google Scholar 

  12. Glorius M, Moll H and Bernhard G 2008 Complexation of curium (III) with hydroxamic acids investigated by time-resolved laser-induced fluorescence spectroscopy Polyhedron 27 2113

  13. Tkac P Matteson B Bruso J and Paulenova A 2008 Complexation of uranium (VI) with acetohydroxamic acid J. Radioanal. Nucl. Chem. 277 31

    Article  CAS  Google Scholar 

  14. Madic C Lecomte M, Baron P and Boullis B 2002 Separation of long-lived radionuclides from high active nuclear waste Comp. Rend. Phys. 3 797

    Article  CAS  Google Scholar 

  15. Rajasekar N and Soundararajan S 1980 Complexes of lanthanide nitrates with 2-N-(6-picoIyl)-benzamide J. Chem. Sci. 89 263

    CAS  Google Scholar 

  16. Nair C G R and Radhakrishnan P K 1981 Complexes of rare earth perchlorates and nitrates with 3-methyl, 1-phenyl, pyrazol-5-one J. Chem. Sci. 90 541

    CAS  Google Scholar 

  17. Muller Julie M, Galley Shane S, Albrecht-Schmitt Thomas E and Nash Kenneth L 2016 Characterization of lanthanide complexes with bis-1, 2, 3-triazole-bipyridine ligands involved in actinide/lanthanide separation Inorg. Chem. 55 11454

    CAS  Google Scholar 

  18. Chacko J, Prabhakaran C P and Nair C G R 1975 Complexes Of La(III), Pr(III), Nd(III), Sm(III), Gd(III), Dy(III) & Y(III) With 4-Aminoantipyrine Inorg. Chem. 13 411

    CAS  Google Scholar 

  19. Kakkar R 2013 Theoretical studies on hydroxamic acids (Berlin: Springer)

    Book  Google Scholar 

  20. Adiguzel E, Yilmaz F, Emirik M and Ozil M 2017 Synthesis and characterization of two new hydroxamic acids derivatives and their metal complexes. An investigation on the keto/enol, E/Z and hydroxamate/hydroximate forms J. Mol. Struct. 1127 403

  21. Tian M, Song N, Wang D, Quan X, Jia Q, Liao W and Lin L 2012 Applications of the binary mixture of sec-octylphenoxyacetic acid and 8-hydroxyquinoline to the extraction of rare earth elements Hydrometallurgy 111–112 109

  22. Sarvaramini A, Azizi D and Larachi F 2016 Hydroxamic acid interactions with solvated cerium hydroxides in the flotation of monazite and bastnäsite—experiments and DFT study Appl. Surf. Sci. 387 986

    Article  CAS  Google Scholar 

  23. Azizi D and Larachi F 2018 Surface interactions and flotation behavior of calcite, dolomite and ankerite with alkyl hydroxamic acid bearing collector and sodium silicate Colloid. Surf. A 537 126

    Article  CAS  Google Scholar 

  24. Zhao G, Zhong H, Qiu X, Wang S, Gao Y, Dai Z, Huang J and Liu G 2013 The DFT study of cyclohexyl hydroxamic acid as a collector in scheelite flotation Mineral. Eng. 49 54

    Google Scholar 

  25. Miaomiao T, Qiong J and Wuping L 2013 Studies on synergistic solvent extraction of rare earth elements from nitrate medium by mixtures of 8-hydroxyquinoline with Cyanex 301 or Cyanex 302 J. Rare Earths 31 604

    Article  Google Scholar 

  26. Kakkar R, Grover R and Gahlot P 2006 Metal ion selectivity of hydroxamates: a density functional study J. Mol. Struct. Theochem. 767 175

    Article  CAS  Google Scholar 

  27. Gupta 2013 Hydroxamic Acids: A Unique Family of Chemicals with Multiple Biological Activities P Satya (Ed.) (Berlin: Springer) pp. 281-309

  28. Gujar R B, Ansari S A, Sengupta A, Murali M S and Mohapatra P K 2016 Extractive complexation of lanthanides and Am (III) by 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone in ionic liquid: Solvent extraction and spectroscopic studies Inorg. Chem. Commun. 73 72

    CAS  Google Scholar 

  29. Rout A, Venkatesan K A and Antony M P 2016 Extraction behavior of Am (III) and Eu (III) in 1, 3-diketonate based ionic liquid J. Radioanal. Nucl. Chem. 310 91

    Article  CAS  Google Scholar 

  30. Urbanski T S, Fornari P, and Abbruzzese C 1996 The extraction of cerium (III) and lanthanum (III) from chloride solutions with LIX 54 Hydrometallurgy 40 169

  31. Gans P, Sabatini A and Vacca A 1996 Investigation of equilibria in solution. Determination of equilibrium constants with the HYPERQUAD suite of programs Talanta 43 1739

    CAS  PubMed  Google Scholar 

  32. Becke A D 1993 A new mixing of Hartree–Fock and local density‐functional theories J. Chem. Phys. 98 1372

    Article  CAS  Google Scholar 

  33. Weigend F and Ahlrichs R 2005 Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy Phys. Chem. Chem. Phys. 7 3297

    Article  CAS  Google Scholar 

  34. Schafer A, Horn H and Ahlrichs R 1994 Fully optimized contracted Gaussian basis sets of triple zeta valence quality for atoms Li to Kr J. Chem. Phys. 97 2571

    Article  Google Scholar 

  35. Kreutzer Johannes, Blaha Peter and Schubert Ulrich 2016 Assessment of different basis sets and DFT functionals for the calculation of structural parameters, vibrational modes and ligand binding energies of Zr4O2(carboxylate)12 clusters Comput. Theor. Chem. 1084 162

    Article  Google Scholar 

  36. Balasubramani S G, Chen Guo P, Sonia C, Diedenhofen M, Frank Marius S, Franzke Yannick J, Filipp F, Grotjahn R, Harding Michael E, Hattig C, Hellweg A, Helmich-Paris B, Holzer C, Huniar U, Kaupp M, Khah A M, Khani S K, Muller T, Mack F, Nguyen Brian D, Parker Shane M, Perlt Eva, Rappoport D, Reiter K, Roy S, Ruckert M, Schmitz G, Sierka M, Tapavicza E, Tew David P, Wullen Christoph van, Voora Vamsee K, Weigend F, Wodynski A and Yu Jason M 2020 TURBOMOLE: Modular program suite for ab initio quantum-chemical and condensed-matter simulations J. Chem. Phys. 152 184107

  37. Abdul R A 2011 Gabedit—A graphical user interface for computational chemistry softwares J. Comput. Chem. 174–182 2011

    Google Scholar 

  38. Kaczor A and Proniewicz L M 2004 The structural study of acetohydroxamic and oxalodihydroxamic acids in DMSO solution based on the DFT calculations of NMR spectra J. Mol. Struct. 704 189

    Article  CAS  Google Scholar 

  39. Magdalena S and Zofia M 2007 Keto–iminol tautomerism in acetohydroxamic and formohydroxamic acids Experimental and theoretical study Vibrat. Spectrosc. 45 46

    Google Scholar 

  40. Migdisov Art A and Williams-Jones A E 2008 A spectrophotometric study of Nd (III), Sm (III) and Er (III) complexation in sulfate-bearing solutions at elevated temperatures Geochim. Cosmochim. Acta 72 5291

    Article  Google Scholar 

  41. Stepanchikova S A and Kolonin G R 1999 Spectrophotometric Study of Complex Formation Ьy Neodymium in Chloride Solutions at Temperatures up to 250 °C Russ. J. Inorg. Chem. 44 10

    Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Metallurgical and Materials Engineering, Indian Institute of Technology Kharagpur, Kharagpur, 721302, West Bengal, India

    Anindita Pati & T K Kundu

  2. Radiochemistry Division, Trombay, Bhabha Atomic Research Centre, BARC, Mumbai, 400085, Maharashtra, India

    Arunasis Bhattacharyya & P K Pujari

  3. Department of Metallurgical and Materials Engineering, National Institute of Technology Rourkela, Rourkela, 769008, Odisha, India

    Snehanshu Pal

Authors
  1. Anindita Pati
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Arunasis Bhattacharyya
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. P K Pujari
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Snehanshu Pal
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. T K Kundu
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Anindita Pati.

Additional information

The original online version of this article was revised: to include the author Snehanshu Pal and to include the affiliation for author T. K. Kundu.

Supplementary Information

Below is the link to the electronic supplementary material.

Supplementary file1 (PDF 3184 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Pati, A., Bhattacharyya, A., Pujari, P.K. et al. Investigation of lanthanide complexation with acetohydroxamic acid in nitrate medium: experimental and DFT studies. J Chem Sci 133, 60 (2021). https://doi.org/10.1007/s12039-021-01927-0

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s12039-021-01927-0

Keywords

Search

Navigation