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On the Heterogeneous Nature of Cisplatin‐1‐Methyluracil Complexes: Coexistence of Different Aggregation Modes and Partial Loss of NH 3 Ligands as Likely Explanation


Pullen, Sonja; Hegmans, Alexander; Hiller, Wolf G; Platzek, André; Freisinger, Eva; Lippert, Bernhard (2021). On the Heterogeneous Nature of Cisplatin‐1‐Methyluracil Complexes: Coexistence of Different Aggregation Modes and Partial Loss of NH 3 Ligands as Likely Explanation. ChemistryOpen, 10(1):28-45.

Abstract

The conversion of the 1 : 1-complex of Cisplatin with 1-methyluracil (1MeUH), cis-[Pt(NH3)2(1MeU-N3)Cl] (1 a) to the aqua species cis-[Pt(NH3)2(1MeU-N3)(OH2)]+ (1 b), achieved by reaction of 1 a with AgNO3 in water, affords a mixture of compounds, the composition of which strongly depends on sample history. The complexity stems from variations in condensation patterns and partial loss of NH3 ligands. In dilute aqueous solution, 1 a, and dinuclear compounds cis-[(NH3)2(1MeU-N3)Pt(μ-OH)Pt(1MeU-N3)(NH3)2]+(3) as well as head-tail cis-[Pt2(NH3)4(μ-1MeU-N3,O4)2]2+ (4) represent the major components. In addition, there are numerous other species present in minor quantities, which differ in metal nuclearity, stoichiometry, stereoisomerism, and Pt oxidation state, as revealed by a combination of 1H NMR and ESI-MS spectroscopy. Their composition appears not to be the consequence of a unique and repeating coordination pattern of the 1MeU ligand in oligomers but rather the coexistence of distinctly different condensation patterns, which include μ-OH, μ-1MeU, and μ-NH2 bridging and combinations thereof. Consequently, the products obtained should, in total, be defined as a heterogeneous mixture rather than a mixture of oligomers of different sizes. In addition, a N2 complex, [Pt(NH3)(1MeU)(N2)]+ appears to be formed in gas phase during the ESI-MS experiment. In the presence of Na+ ions, multimers n of 1 a with n=2, 3, 4 are formed that represent analogues of non-metalated uracil quartets found in tetrastranded RNA.

Abstract

The conversion of the 1 : 1-complex of Cisplatin with 1-methyluracil (1MeUH), cis-[Pt(NH3)2(1MeU-N3)Cl] (1 a) to the aqua species cis-[Pt(NH3)2(1MeU-N3)(OH2)]+ (1 b), achieved by reaction of 1 a with AgNO3 in water, affords a mixture of compounds, the composition of which strongly depends on sample history. The complexity stems from variations in condensation patterns and partial loss of NH3 ligands. In dilute aqueous solution, 1 a, and dinuclear compounds cis-[(NH3)2(1MeU-N3)Pt(μ-OH)Pt(1MeU-N3)(NH3)2]+(3) as well as head-tail cis-[Pt2(NH3)4(μ-1MeU-N3,O4)2]2+ (4) represent the major components. In addition, there are numerous other species present in minor quantities, which differ in metal nuclearity, stoichiometry, stereoisomerism, and Pt oxidation state, as revealed by a combination of 1H NMR and ESI-MS spectroscopy. Their composition appears not to be the consequence of a unique and repeating coordination pattern of the 1MeU ligand in oligomers but rather the coexistence of distinctly different condensation patterns, which include μ-OH, μ-1MeU, and μ-NH2 bridging and combinations thereof. Consequently, the products obtained should, in total, be defined as a heterogeneous mixture rather than a mixture of oligomers of different sizes. In addition, a N2 complex, [Pt(NH3)(1MeU)(N2)]+ appears to be formed in gas phase during the ESI-MS experiment. In the presence of Na+ ions, multimers n of 1 a with n=2, 3, 4 are formed that represent analogues of non-metalated uracil quartets found in tetrastranded RNA.

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Item Type:Journal Article, not_refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Scopus Subject Areas:Physical Sciences > General Chemistry
Uncontrolled Keywords:General Chemistry
Language:English
Date:1 January 2021
Deposited On:14 Feb 2022 15:59
Last Modified:19 Jun 2024 03:30
Publisher:Wiley Open Access
ISSN:2191-1363
OA Status:Gold
Free access at:Publisher DOI. An embargo period may apply.
Publisher DOI:https://doi.org/10.1002/open.202000317
  • Content: Published Version
  • Licence: Creative Commons: Attribution-NonCommercial 4.0 International (CC BY-NC 4.0)