ArticleChemical science2023
Kinetics of ligand exchange in solution: a quantitative mass spectrometry approach.
Article in Chemical science, 2023. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 4 papers.
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Who cites it
4 citing papers in PubMed, 9 citations in OpenAlex.
- Aluminum Cross-Linked Carboxylated Nanocellulose Hydrogels with Enhanced Antifreezing Properties.ACS omega · 2026Article
- Is the Signal Worth the Noise? A Practical Guide to Charge-Tagging for ESI-MS Reaction Monitoring.ACS organic & inorganic Au · 2026Article
- Quantitative Online Monitoring of an Immobilized Enzymatic Network by Ion Mobility-Mass Spectrometry.Journal of the American Chemical Society · 2024Article
- Competing Mechanisms in Palladium-Catalyzed Alkoxycarbonylation of Styrene.ACS catalysis · 2024Article
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Authors and funding
4 authors at 1 institution in 1 country.
Funding
No grant is acknowledged in the PubMed record.
Abstract
Complex speciation and exchange kinetics of labile ligands are critical parameters for understanding the reactivity of metal complexes in solution. We present a novel approach to determine ligand exchange parameters based on electrospray ionization mass spectrometry (ESI-MS). The introduction of isotopically labelled ligands to a solution of metal host and unlabelled ligands allows the quantitative investigation of the solution-phase equilibria. Furthermore, ion mobility separation can target individual isomers, such as ligands bound at specific sites. As a proof of concept, we investigate the solution equilibria of labile pyridine ligands coordinated in the cavity of macrocyclic porphyrin cage complexes bearing diamagnetic or paramagnetic metal centres. The effects of solvent, porphyrin coordination sphere, transition metal, and counterion on ligand dissociation are discussed. Rate constants and activation parameters for ligand dissociation in the solution can be derived from our ESI-MS approach, thereby providing mechanistic insights that are not easily obtained from traditional solution-phase techniques.
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Registered trials
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