Issue 36, 2023

Kinetics of ligand exchange in solution: a quantitative mass spectrometry approach

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.

Graphical abstract: Kinetics of ligand exchange in solution: a quantitative mass spectrometry approach

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Article information

Article type
Edge Article
Submitted
30 jun 2023
Accepted
24 aug 2023
First published
24 aug 2023
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2023,14, 9759-9769

Kinetics of ligand exchange in solution: a quantitative mass spectrometry approach

Q. Duez, P. Tinnemans, J. A. A. W. Elemans and J. Roithová, Chem. Sci., 2023, 14, 9759 DOI: 10.1039/D3SC03342B

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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