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<p>Interactions of the citrate complexes [V<sup>IV</sup><sub>2</sub>O<sub>2</sub>(citr)<sub>2</sub>]<sup>4−</sup> and their protonated forms bearing polymer chains, which include vinylphosphonic acid and acrylamide units containing functional —P(O)(OH)<sub>2</sub> and —C(O)NH<sub>2</sub> groups, were studied by the DFT method at the M06/def2tzvp level of theory. The experimental IR spectra show V—O(P) stretching bands involving vanadium atoms of the coordination anion [V<sub>2</sub>O<sub>2</sub>(C<sub>6</sub>H<sub>4</sub>O<sub>7</sub>)<sub>2</sub>]<sup>4−</sup> and the phosphonate oxygen atom of the copolymer —P(O)(OH)(O—)<sup>1−</sup>. The formation of the V—O(P) bond between the metal complex and the phosphonate anion of the copolymer was found to be due to the presence of —CO<sub>2</sub>H groups in the ligand environment of divanadium citrate, resulting in a decrease in the overall negative charge of the complex. Experimentally, this corresponds to the controlled protonation of the citrate ligands of the starting metal complex. In the resulting [V<sub>2</sub>O<sub>2</sub>(C<sub>6</sub>H<sub>5</sub>O<sub>7</sub>)<sub>2</sub>]<sup>2−</sup> and [V<sub>2</sub>O<sub>2</sub>(C<sub>6</sub>H<sub>6</sub>O<sub>7</sub>)<sub>2</sub>]<sup>0</sup> complexes, the opening of two to four chelate rings results in the formation of additional reaction sites for the binding of complexing metals to anionic phosphonate groups. The V—O(P) stretching vibrations in the calculated IR spectrum for the formation of [V<sub>2</sub>O<sub>2</sub>(C<sub>6</sub>H<sub>5</sub>O<sub>7</sub>)<sub>2</sub>]<sup>2−</sup> are similar to the experimental values.</p>

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Formation of a water-soluble vanadium(iv) metal-polymer complex with a copolymer of vinylphosphonic acid and acrylamide: DFT quantum chemical modeling

  • 期刊论文

  • 发表日期：

    2025年6月1日

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  • D. O. Ruzanov,
  • A. I. Fischer,
  • N. S. Panina,
  • Ye. F. Panarin

摘要

Interactions of the citrate complexes [VIV2O2(citr)2]4− and their protonated forms bearing polymer chains, which include vinylphosphonic acid and acrylamide units containing functional —P(O)(OH)2 and —C(O)NH2 groups, were studied by the DFT method at the M06/def2tzvp level of theory. The experimental IR spectra show V—O(P) stretching bands involving vanadium atoms of the coordination anion [V2O2(C6H4O7)2]4− and the phosphonate oxygen atom of the copolymer —P(O)(OH)(O—)1−. The formation of the V—O(P) bond between the metal complex and the phosphonate anion of the copolymer was found to be due to the presence of —CO2H groups in the ligand environment of divanadium citrate, resulting in a decrease in the overall negative charge of the complex. Experimentally, this corresponds to the controlled protonation of the citrate ligands of the starting metal complex. In the resulting [V2O2(C6H5O7)2]2− and [V2O2(C6H6O7)2]0 complexes, the opening of two to four chelate rings results in the formation of additional reaction sites for the binding of complexing metals to anionic phosphonate groups. The V—O(P) stretching vibrations in the calculated IR spectrum for the formation of [V2O2(C6H5O7)2]2− are similar to the experimental values.