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Type: Artigo
Title: Can mass dissociation patterns of transition-metal complexes be predicted from electrochemical data?
Author: Toma, Sergio H.
Alexiou, Anamaria D. P.
Toma, Henrique E.
Araki, Koiti
Eberlin, Marcos N.
Abstract: The Cooks kinetic method has been very convenient to correlate the relative dissociation rates obtained by collision‐induced fragmentation experiments with the energies of two related bonds in molecules and complexes in the gas phase. Reliable bond energy data are, however, not always available, particularly for polynuclear transition‐metal complexes, such as the triruthenium acetate clusters of the general formula [Ru3 (µ3‐O)(µ‐CH3COO)6(py)2(L)]+, where L = ring substituted N‐heterocyclic ligands. Accordingly, their gas‐phase collision‐induced tandem mass spectrometry (CID MS/MS) dissociation patterns have been analyzed pursuing a relationship with the more easily accessible redox potentials (E1/2) and Lever's EL parameters. In fact, excellent linear correlations of ln(1/2AL/Apy), where Apy and AL are the abundance of the fragments retaining the pyridine (py) and L ligand, respectively, with E1/2 and EL were found. This result shows that those electrochemical parameters are correlated with bond energies and can be used in the analysis of the dissociation data. Such modified Cooks method can be used, for example, to determine the electronic effects of substituents on the metal–ligand bonds for a series of transition‐metal complexes
Subject: Espectrometria de massa
Country: Reino Unido
Editor: John Wiley & Sons
Rights: Fechado
Identifier DOI: 10.1002/jms.1513
Date Issue: 2009
Appears in Collections:IQ - Artigos e Outros Documentos

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