Effect of the Additional Carboxyl Group in Half-Sandwich Organometallic 2,4-Dipicolinate Complexes on Solution Speciation and Structure
Authors
Mészáros, János P.Németi, Gábor
Poljarević, Jelena
Holczbauer, Tamás
May, Nóra V.
Enyedy, Éva A.
Article (Published version)
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Solution speciation of Rh(η5-C5Me5), Ru(η6-p-cymene) and Ru(η6-toluene) complexes of 2,4-pyridinedicarboxylic acid (2,4-dipicH2) was studied and compared to that of 2-picolinic acid (picH) in addition to their reactivity towards chloride and bromide ions, 1-methylimidazole and guanosine. Structures of [Rh(η5-C5Me5)(2,4-dipicH)Cl] ⋅ 3H2O (1), 2[Ru(η6-toluene)(2,4-dipicH)Cl] ⋅ 3H2O (2) and [Ru(η6-toluene)(2,4-dipic)]3 ⋅ 7H2O (3) were analyzed by X-ray diffraction. 1 and 2 show typical piano stool geometry, while 3 is a triangular complex stabilized via the monodentate coordination of the second carboxylate group to the neighboring Ru(II) center. High stability [M(arene)L(H2O/Cl)] species predominate at pH 7.4. 2,4-Dipic forms more stable complexes with Ru(η6-arene) than pic, with this difference being minor in the case of the Rh(η5-C5Me5) complexes. A lower affinity of 2,4-dipic complexes to halide ions was found compared to the corresponding pic complexes due to the additional COO− moie...ty.
Keywords:
2-picolinic acid / Halide affinity / Solution stability / Trinuclear complex / X-ray crystal structuresSource:
European Journal of Inorganic Chemistry, 2021, 2021, 19, 1858-1868Publisher:
- Wiley
Funding / projects:
- NationalResearch,DevelopmentandInnovationOffice-NKFIA (FK124240,KH129588PD128504)
- Ministry of Human Capacities (ÚNKP-20-3-SZTE-544, TKP-2020)
- University of Szeged Open Access Fund (5302)
DOI: 10.1002/ejic.202100122
ISSN: 1434-1948
WoS: 000647914400001
Scopus: 2-s2.0-85105372805
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Hemijski fakultet / Faculty of ChemistryTY - JOUR AU - Mészáros, János P. AU - Németi, Gábor AU - Poljarević, Jelena AU - Holczbauer, Tamás AU - May, Nóra V. AU - Enyedy, Éva A. PY - 2021 UR - http://cherry.chem.bg.ac.rs/handle/123456789/4815 AB - Solution speciation of Rh(η5-C5Me5), Ru(η6-p-cymene) and Ru(η6-toluene) complexes of 2,4-pyridinedicarboxylic acid (2,4-dipicH2) was studied and compared to that of 2-picolinic acid (picH) in addition to their reactivity towards chloride and bromide ions, 1-methylimidazole and guanosine. Structures of [Rh(η5-C5Me5)(2,4-dipicH)Cl] ⋅ 3H2O (1), 2[Ru(η6-toluene)(2,4-dipicH)Cl] ⋅ 3H2O (2) and [Ru(η6-toluene)(2,4-dipic)]3 ⋅ 7H2O (3) were analyzed by X-ray diffraction. 1 and 2 show typical piano stool geometry, while 3 is a triangular complex stabilized via the monodentate coordination of the second carboxylate group to the neighboring Ru(II) center. High stability [M(arene)L(H2O/Cl)] species predominate at pH 7.4. 2,4-Dipic forms more stable complexes with Ru(η6-arene) than pic, with this difference being minor in the case of the Rh(η5-C5Me5) complexes. A lower affinity of 2,4-dipic complexes to halide ions was found compared to the corresponding pic complexes due to the additional COO− moiety. PB - Wiley T2 - European Journal of Inorganic Chemistry T1 - Effect of the Additional Carboxyl Group in Half-Sandwich Organometallic 2,4-Dipicolinate Complexes on Solution Speciation and Structure VL - 2021 IS - 19 SP - 1858 EP - 1868 DO - 10.1002/ejic.202100122 ER -
@article{ author = "Mészáros, János P. and Németi, Gábor and Poljarević, Jelena and Holczbauer, Tamás and May, Nóra V. and Enyedy, Éva A.", year = "2021", abstract = "Solution speciation of Rh(η5-C5Me5), Ru(η6-p-cymene) and Ru(η6-toluene) complexes of 2,4-pyridinedicarboxylic acid (2,4-dipicH2) was studied and compared to that of 2-picolinic acid (picH) in addition to their reactivity towards chloride and bromide ions, 1-methylimidazole and guanosine. Structures of [Rh(η5-C5Me5)(2,4-dipicH)Cl] ⋅ 3H2O (1), 2[Ru(η6-toluene)(2,4-dipicH)Cl] ⋅ 3H2O (2) and [Ru(η6-toluene)(2,4-dipic)]3 ⋅ 7H2O (3) were analyzed by X-ray diffraction. 1 and 2 show typical piano stool geometry, while 3 is a triangular complex stabilized via the monodentate coordination of the second carboxylate group to the neighboring Ru(II) center. High stability [M(arene)L(H2O/Cl)] species predominate at pH 7.4. 2,4-Dipic forms more stable complexes with Ru(η6-arene) than pic, with this difference being minor in the case of the Rh(η5-C5Me5) complexes. A lower affinity of 2,4-dipic complexes to halide ions was found compared to the corresponding pic complexes due to the additional COO− moiety.", publisher = "Wiley", journal = "European Journal of Inorganic Chemistry", title = "Effect of the Additional Carboxyl Group in Half-Sandwich Organometallic 2,4-Dipicolinate Complexes on Solution Speciation and Structure", volume = "2021", number = "19", pages = "1858-1868", doi = "10.1002/ejic.202100122" }
Mészáros, J. P., Németi, G., Poljarević, J., Holczbauer, T., May, N. V.,& Enyedy, É. A.. (2021). Effect of the Additional Carboxyl Group in Half-Sandwich Organometallic 2,4-Dipicolinate Complexes on Solution Speciation and Structure. in European Journal of Inorganic Chemistry Wiley., 2021(19), 1858-1868. https://doi.org/10.1002/ejic.202100122
Mészáros JP, Németi G, Poljarević J, Holczbauer T, May NV, Enyedy ÉA. Effect of the Additional Carboxyl Group in Half-Sandwich Organometallic 2,4-Dipicolinate Complexes on Solution Speciation and Structure. in European Journal of Inorganic Chemistry. 2021;2021(19):1858-1868. doi:10.1002/ejic.202100122 .
Mészáros, János P., Németi, Gábor, Poljarević, Jelena, Holczbauer, Tamás, May, Nóra V., Enyedy, Éva A., "Effect of the Additional Carboxyl Group in Half-Sandwich Organometallic 2,4-Dipicolinate Complexes on Solution Speciation and Structure" in European Journal of Inorganic Chemistry, 2021, no. 19 (2021):1858-1868, https://doi.org/10.1002/ejic.202100122 . .