期刊
JOURNAL OF MASS SPECTROMETRY
卷 44, 期 3, 页码 361-367出版社
WILEY
DOI: 10.1002/jms.1513
关键词
Cooks kinetic method; mass spectrometry; electrospray; MS/MS dissociation; ruthenium acetate clusters; E-L parameters
资金
- Sao Paulo State research foundation (FAPESP)
- Brazilian national research council (CNPq)
- Instituto do Milenio de Materiais Complexos
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-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 (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.
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