Can mass dissociation patterns of transition-metal complexes be predicted from electrochemical data?
Contribuinte(s) |
UNIVERSIDADE DE SÃO PAULO |
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Data(s) |
20/10/2012
20/10/2012
2009
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Resumo |
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 [Ru(3) (mu(3)-O)(mu-CH(3)COO)(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 (E(1/2)) and Lever`s E(L) parameters. In fact, excellent linear correlations of In(1/2A(L)/A(py)), where A(py) and A(L) are the abundance of the fragments retaining the pyridine (py) and L ligand, respectively, with E(1/2) and E(L) 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. Copyright (C) 2008 John Wiley & Sons, Ltd. Sao Paulo State research foundation (FAPESP) Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) Brazilian national research council (CNPq) Instituto do Milenio de Materiais Complexos Instituto do Milenio de Materiais Complexos |
Identificador |
JOURNAL OF MASS SPECTROMETRY, v.44, n.3, p.361-367, 2009 1076-5174 http://producao.usp.br/handle/BDPI/31217 10.1002/jms.1513 |
Idioma(s) |
eng |
Publicador |
JOHN WILEY & SONS LTD |
Relação |
Journal of Mass Spectrometry |
Direitos |
restrictedAccess Copyright JOHN WILEY & SONS LTD |
Palavras-Chave | #Cooks kinetic method #mass spectrometry #electrospray #MS/MS dissociation #ruthenium acetate clusters #E(L) parameters #KINETIC METHOD #RUTHENIUM CLUSTER #ACETATE CLUSTERS #ELECTROSPRAY MASS #REDOX POTENTIALS #TETRARUTHENATED PORPHYRINS #TRIRUTHENIUM CLUSTERS #COBALT PORPHYRIN #SPECTROMETRY #AFFINITIES #Biophysics #Chemistry, Organic #Spectroscopy |
Tipo |
article original article publishedVersion |