Interaction between [(η<sup>6</sup>-<i>p</i>-cym)M(H<sub>2</sub>O)<sub>3</sub>]<sup>2+</sup> (M<sup>II</sup> = Ru, Os) or [(η<sup>5</sup>-Cp*)M(H<sub>2</sub>O)<sub>3</sub>]<sup>2+</sup> (M<sup>III</sup> = Rh, Ir) and Phosphonate Derivatives of Iminodiacetic Acid: A Solution Equilibrium and DFT Study
The pH-dependent binding strengths and modes of the organometallic [(η<sup>6</sup>-<i>p</i>-cym)M(H<sub>2</sub>O)<sub>3</sub>]<sup>2+</sup> (M<sup>II</sup> = Ru, Os; <i>p</i>-cym = 1-methyl-4-isopropylbenzene) or [(η...
| Main Authors: | , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2023-02-01
|
| Series: | Molecules |
| Subjects: | |
| Online Access: | https://www.mdpi.com/1420-3049/28/3/1477 |
| _version_ | 1797623707911323648 |
|---|---|
| author | Linda Bíró Botond Tóth Norbert Lihi Etelka Farkas Péter Buglyó |
| author_facet | Linda Bíró Botond Tóth Norbert Lihi Etelka Farkas Péter Buglyó |
| author_sort | Linda Bíró |
| collection | DOAJ |
| description | The pH-dependent binding strengths and modes of the organometallic [(η<sup>6</sup>-<i>p</i>-cym)M(H<sub>2</sub>O)<sub>3</sub>]<sup>2+</sup> (M<sup>II</sup> = Ru, Os; <i>p</i>-cym = 1-methyl-4-isopropylbenzene) or [(η<sup>5</sup>-Cp*)M(H<sub>2</sub>O)<sub>3</sub>]<sup>2+</sup> (M<sup>III</sup> = Rh, Ir; Cp* = pentamethylcyclopentadienyl anion) cations towards iminodiacetic acid (H<sub>2</sub>Ida) and its biorelevant mono- and diphosphonate derivatives N-(phosphonomethyl)-glycine (H<sub>3</sub>IdaP) and iminodi(methylphosphonic acid) (H<sub>4</sub>Ida2P) was studied in an aqueous solution. The results showed that all three of the ligands form 1:1 complexes via the tridentate (O,N,O) donor set, for which the binding mode was further corroborated by the DFT method. Although with IdaP<sup>3−</sup> and Ida2P<sup>4−</sup> in mono- and bis-protonated species, where H<sup>+</sup> might also be located at the non-coordinating N atom, the theoretical calculations revealed the protonation of the phosphonate group(s) and the tridentate coordination of the phosphonate ligands. The replacement of one carboxylate in Ida<sup>2−</sup> by a phosphonate group (IdaP<sup>3−</sup>) resulted in a significant increase in the stability of the metal complexes; however, this increase vanished with Ida2P<sup>4−</sup>, which was most likely due to some steric hindrance upon the coordination of the second large phosphonate group to form (5 + 5) joined chelates. In the phosphonate-containing systems, the neutral 1:1 complexes are the major species at pH 7.4 in the millimolar concentration range that is supported by both NMR and ESI-TOF-MS. |
| first_indexed | 2024-03-11T09:32:37Z |
| format | Article |
| id | doaj.art-a9f8b4d14b01402aa4401f780065dbce |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-11T09:32:37Z |
| publishDate | 2023-02-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-a9f8b4d14b01402aa4401f780065dbce2023-11-16T17:33:04ZengMDPI AGMolecules1420-30492023-02-01283147710.3390/molecules28031477Interaction between [(η<sup>6</sup>-<i>p</i>-cym)M(H<sub>2</sub>O)<sub>3</sub>]<sup>2+</sup> (M<sup>II</sup> = Ru, Os) or [(η<sup>5</sup>-Cp*)M(H<sub>2</sub>O)<sub>3</sub>]<sup>2+</sup> (M<sup>III</sup> = Rh, Ir) and Phosphonate Derivatives of Iminodiacetic Acid: A Solution Equilibrium and DFT StudyLinda Bíró0Botond Tóth1Norbert Lihi2Etelka Farkas3Péter Buglyó4Department of Inorganic & Analytical Chemistry, Faculty of Science and Technology, University of Debrecen, Egyetem tér 1, H-4032 Debrecen, HungaryDepartment of Inorganic & Analytical Chemistry, Faculty of Science and Technology, University of Debrecen, Egyetem tér 1, H-4032 Debrecen, HungaryDepartment of Inorganic & Analytical Chemistry, Faculty of Science and Technology, University of Debrecen, Egyetem tér 1, H-4032 Debrecen, HungaryDepartment of Inorganic & Analytical Chemistry, Faculty of Science and Technology, University of Debrecen, Egyetem tér 1, H-4032 Debrecen, HungaryDepartment of Inorganic & Analytical Chemistry, Faculty of Science and Technology, University of Debrecen, Egyetem tér 1, H-4032 Debrecen, HungaryThe pH-dependent binding strengths and modes of the organometallic [(η<sup>6</sup>-<i>p</i>-cym)M(H<sub>2</sub>O)<sub>3</sub>]<sup>2+</sup> (M<sup>II</sup> = Ru, Os; <i>p</i>-cym = 1-methyl-4-isopropylbenzene) or [(η<sup>5</sup>-Cp*)M(H<sub>2</sub>O)<sub>3</sub>]<sup>2+</sup> (M<sup>III</sup> = Rh, Ir; Cp* = pentamethylcyclopentadienyl anion) cations towards iminodiacetic acid (H<sub>2</sub>Ida) and its biorelevant mono- and diphosphonate derivatives N-(phosphonomethyl)-glycine (H<sub>3</sub>IdaP) and iminodi(methylphosphonic acid) (H<sub>4</sub>Ida2P) was studied in an aqueous solution. The results showed that all three of the ligands form 1:1 complexes via the tridentate (O,N,O) donor set, for which the binding mode was further corroborated by the DFT method. Although with IdaP<sup>3−</sup> and Ida2P<sup>4−</sup> in mono- and bis-protonated species, where H<sup>+</sup> might also be located at the non-coordinating N atom, the theoretical calculations revealed the protonation of the phosphonate group(s) and the tridentate coordination of the phosphonate ligands. The replacement of one carboxylate in Ida<sup>2−</sup> by a phosphonate group (IdaP<sup>3−</sup>) resulted in a significant increase in the stability of the metal complexes; however, this increase vanished with Ida2P<sup>4−</sup>, which was most likely due to some steric hindrance upon the coordination of the second large phosphonate group to form (5 + 5) joined chelates. In the phosphonate-containing systems, the neutral 1:1 complexes are the major species at pH 7.4 in the millimolar concentration range that is supported by both NMR and ESI-TOF-MS.https://www.mdpi.com/1420-3049/28/3/1477IDA-based phosphonatesorganorutheniumorganorhodiumsolution equilibriumcomplex |
| spellingShingle | Linda Bíró Botond Tóth Norbert Lihi Etelka Farkas Péter Buglyó Interaction between [(η<sup>6</sup>-<i>p</i>-cym)M(H<sub>2</sub>O)<sub>3</sub>]<sup>2+</sup> (M<sup>II</sup> = Ru, Os) or [(η<sup>5</sup>-Cp*)M(H<sub>2</sub>O)<sub>3</sub>]<sup>2+</sup> (M<sup>III</sup> = Rh, Ir) and Phosphonate Derivatives of Iminodiacetic Acid: A Solution Equilibrium and DFT Study Molecules IDA-based phosphonates organoruthenium organorhodium solution equilibrium complex |
| title | Interaction between [(η<sup>6</sup>-<i>p</i>-cym)M(H<sub>2</sub>O)<sub>3</sub>]<sup>2+</sup> (M<sup>II</sup> = Ru, Os) or [(η<sup>5</sup>-Cp*)M(H<sub>2</sub>O)<sub>3</sub>]<sup>2+</sup> (M<sup>III</sup> = Rh, Ir) and Phosphonate Derivatives of Iminodiacetic Acid: A Solution Equilibrium and DFT Study |
| title_full | Interaction between [(η<sup>6</sup>-<i>p</i>-cym)M(H<sub>2</sub>O)<sub>3</sub>]<sup>2+</sup> (M<sup>II</sup> = Ru, Os) or [(η<sup>5</sup>-Cp*)M(H<sub>2</sub>O)<sub>3</sub>]<sup>2+</sup> (M<sup>III</sup> = Rh, Ir) and Phosphonate Derivatives of Iminodiacetic Acid: A Solution Equilibrium and DFT Study |
| title_fullStr | Interaction between [(η<sup>6</sup>-<i>p</i>-cym)M(H<sub>2</sub>O)<sub>3</sub>]<sup>2+</sup> (M<sup>II</sup> = Ru, Os) or [(η<sup>5</sup>-Cp*)M(H<sub>2</sub>O)<sub>3</sub>]<sup>2+</sup> (M<sup>III</sup> = Rh, Ir) and Phosphonate Derivatives of Iminodiacetic Acid: A Solution Equilibrium and DFT Study |
| title_full_unstemmed | Interaction between [(η<sup>6</sup>-<i>p</i>-cym)M(H<sub>2</sub>O)<sub>3</sub>]<sup>2+</sup> (M<sup>II</sup> = Ru, Os) or [(η<sup>5</sup>-Cp*)M(H<sub>2</sub>O)<sub>3</sub>]<sup>2+</sup> (M<sup>III</sup> = Rh, Ir) and Phosphonate Derivatives of Iminodiacetic Acid: A Solution Equilibrium and DFT Study |
| title_short | Interaction between [(η<sup>6</sup>-<i>p</i>-cym)M(H<sub>2</sub>O)<sub>3</sub>]<sup>2+</sup> (M<sup>II</sup> = Ru, Os) or [(η<sup>5</sup>-Cp*)M(H<sub>2</sub>O)<sub>3</sub>]<sup>2+</sup> (M<sup>III</sup> = Rh, Ir) and Phosphonate Derivatives of Iminodiacetic Acid: A Solution Equilibrium and DFT Study |
| title_sort | interaction between η sup 6 sup i p i cym m h sub 2 sub o sub 3 sub sup 2 sup m sup ii sup ru os or η sup 5 sup cp m h sub 2 sub o sub 3 sub sup 2 sup m sup iii sup rh ir and phosphonate derivatives of iminodiacetic acid a solution equilibrium and dft study |
| topic | IDA-based phosphonates organoruthenium organorhodium solution equilibrium complex |
| url | https://www.mdpi.com/1420-3049/28/3/1477 |
| work_keys_str_mv | AT lindabiro interactionbetweenēsup6supipicymmhsub2subosub3subsup2supmsupiisupruosorēsup5supcpmhsub2subosub3subsup2supmsupiiisuprhirandphosphonatederivativesofiminodiaceticacidasolutionequilibriumanddftstudy AT botondtoth interactionbetweenēsup6supipicymmhsub2subosub3subsup2supmsupiisupruosorēsup5supcpmhsub2subosub3subsup2supmsupiiisuprhirandphosphonatederivativesofiminodiaceticacidasolutionequilibriumanddftstudy AT norbertlihi interactionbetweenēsup6supipicymmhsub2subosub3subsup2supmsupiisupruosorēsup5supcpmhsub2subosub3subsup2supmsupiiisuprhirandphosphonatederivativesofiminodiaceticacidasolutionequilibriumanddftstudy AT etelkafarkas interactionbetweenēsup6supipicymmhsub2subosub3subsup2supmsupiisupruosorēsup5supcpmhsub2subosub3subsup2supmsupiiisuprhirandphosphonatederivativesofiminodiaceticacidasolutionequilibriumanddftstudy AT peterbuglyo interactionbetweenēsup6supipicymmhsub2subosub3subsup2supmsupiisupruosorēsup5supcpmhsub2subosub3subsup2supmsupiiisuprhirandphosphonatederivativesofiminodiaceticacidasolutionequilibriumanddftstudy |