Entropy effects in gas phase ion-molecule association reactions

The kinetics of gas phase reactions of the ions C 5H 5M + (M=V, Co, Ni and Ru) with oxygen (Me 2CO, Me 2O, MeOH, Me 2CHOH, H 2O) and nitrogen (NH 3, NH 2Me, NHMe 2, NMe 3) donor ligands have been studied by Ion Trap Mass Spectrometry. The kinetic data confirm the previously found dependence of the l...

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Bibliographic Details
Published in:Journal of organometallic chemistry 2001-04, Vol.626 (1), p.24-31
Main Authors: Innorta, Giuseppe, Torroni, Sandro, Maranzana, Andrea, Tonachini, Glauco
Format: Article
Language:English
Subjects:
Gas-phase chemistry
Ion-molecule reactions
Kinetics
Mass spectrometry
Metallocenes
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Summary:The kinetics of gas phase reactions of the ions C 5H 5M + (M=V, Co, Ni and Ru) with oxygen (Me 2CO, Me 2O, MeOH, Me 2CHOH, H 2O) and nitrogen (NH 3, NH 2Me, NHMe 2, NMe 3) donor ligands have been studied by Ion Trap Mass Spectrometry. The kinetic data confirm the previously found dependence of the log of the rate constants upon the ligand ionization energy. To get some insight on the origin of the existing barrier to the reaction some experiments were performed at various temperatures; it was found that the kinetic constants increased when the temperature decreased. The results are compatible with an entropy effect on the free energy of activation as also shown by some calculations performed for the reaction of the C 5H 5Fe + ion with water.
ISSN:0022-328X
1872-8561
DOI:10.1016/S0022-328X(00)00945-1