Gas phase reactions of the ion C5H5Fe+: A kinetic study

Innorta, G.; Pontoni, Luca; Torroni, Sandro

doi:10.1016/s1044-0305(97)00286-9

Cited by 14 publications

(8 citation statements)

References 35 publications

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“…In our experiments, pyridine typically forms the most kinetically and thermodynamically favorable adducts with metal complex ions, which suggests a high GPB, DM and polarizability are important characteristics of a strong ligand for divalent metal ions in the gas-phase. An inverse correlation between IP and reaction rates has been demonstrated previously for reactions between C 5 H 5 Fe + and various reagent gases [53], implying the importance of IP as an indicator of gas-phase ligand strength. While we do not have enough data to comment on the importance of IP, the favorable reactivity of acetonitrile indicates that this trend does not hold for the divalent metal complex ions that we have studied.…”

Section: Reagent Gas Considerationssupporting

confidence: 52%

Gas-phase ion–molecule reactions of divalent metal complex ions: Toward coordination structure analysis by mass spectrometry and some intrinsic coordination chemistry along the way

Combariza

Fahey

Milshteyn

et al. 2005

International Journal of Mass Spectrometry

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Section: Reagent Gas Considerationssupporting

confidence: 52%

Gas-phase ion–molecule reactions of divalent metal complex ions: Toward coordination structure analysis by mass spectrometry and some intrinsic coordination chemistry along the way

Combariza

Fahey

Milshteyn

et al. 2005

International Journal of Mass Spectrometry

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“…Let us consider the iron cyclopentadienyl ion's (CpFe ϩ , m/z ϭ 121) reaction with CO. As was observed previously [16,17] and confirmed in this work, CpFe ϩ reacts with CO sequentially:…”

Section: Influence Of the Rf Field On The Ion Energysupporting

confidence: 89%

“…This cluster undergoes ligand-switching reactions with water and oxygen, which are present in neon as residual gases (see Figure 9). It was noticed [17,34] that ions of half-sandwich metallocenes react with electron-donating ligands with rate constants that are inversely proportional to the ligand ionization energies (IEs). In general, bond energies are also inversely proportional to the ligand IEs.…”

Section: Ion Molecule Reactions In the Hp-sqccmentioning

confidence: 99%

The high-pressure segmented quadrupole collision cell (HP-SQCC) as an ion molecule reactor

Guo

Siu

Baranov³

2005

J. Am. Soc. Mass Spectrom.

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A high-pressure 20-segment quadrupole collision cell (HP-SQCC), which replaces a collision cell in a modified triple-quadrupole mass spectrometer is investigated in this work as an ion-molecule reactor with an inherent heat source. The highest working pressure achievable is 20 mTorr. The 20 quadrupole segments permit superimposition of linear axial electric field over the conventional quadrupole field in the radial direction. The axial and radial fields are employed to control ion temperature. Heat is transferred to the reactants through ion frictional heating. The HP-SQCC utilizes a combination of several physicochemical phenomena and an attempt is made to examine a range of ion-molecule reactions. Due to a sufficiently large number of reactive collisions, the reactor is used to promote sequential exothermic ion-molecule reactions. To characterize the performance of the HP-SQCC, the various ion-molecule reactions between the fragment ions of ferrocene ( on-molecule reactions have captured the fascination of mass spectrometrists for a number of decades and have been probed using a variety of instrumentation, including Fourier-transform ion cyclotron resonance spectrometry, ion-trap mass spectrometry, triplequadrupole mass spectrometry and the selected-ion flow tube technique [1]. The conventional triplequadrupole mass spectrometer is a less than perfect instrument for an examination of ion-molecule reactions due to the relatively low pressure achievable in its second quadrupole (Q 2 ), which restricts the number of ion-molecule collisions, and to the limited control of ion energy within Q 2 . Nevertheless, reactions that lead to novel products have been discovered; one such reaction is the ligand-exchange reaction between [Pb(CH 3 ; Pb 2ϩ had previously been described as to be among "a select group of doubly charged metal ions that will not form stable complexes in the gas phase with water" [3].Here we report the first ion-molecule reaction results obtained on a high-pressure 20-segment quadrupole collision cell (HP-SQCC) that functions as the Q 2 in a modified triple-quadrupole mass spectrometer. The highest working pressure achievable is 20 mTorr with neon, about 4 times higher than that achievable on a standard triple-quadrupole instrument. The 20 quadrupole segments permit superimposition of an axial electric field, typically linear, over the conventional quadrupole field in the radial direction [4][5][6]. The HP-SQCC was originally developed for ion-mobility measurements [5,7], where the goal is to maintain the drift field low enough that the ion temperature is not increased significantly. In this study, we are exploring the use of the HP-SQCC as an efficient apparatus for utilizing ion-molecule reactions as an analytical method. The axial and radial fields are employed to control the ion temperature.To characterize the performance of the HP-SQCC, we have elected to use as probes the various ionmolecule reactions between the fragment ions of ferrocene (Cp 2 Fe) as well as cobaltocene (Cp 2 Co) and neutra...

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“…The correlation of reactivity of metal com-plexes with the ionization potential has been suggested recently for singly charged metal complexes. 61 The ligand reactivity trend is very likely dependent on a number of factors that cannot be fully isolated in this study.…”

Section: Ligand Reactivity Trendsmentioning

confidence: 93%

Ion-molecule reactions in a quadrupole ion trap as a probe of the gas-phase structure of metal complexes

1998

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A method is described in which the coordination number in metal complexes can be determined using ion–molecule reactions in a quadrupole ion trap mass spectrometer. Complexes of first‐row transition metals in the +2 oxidation state, including manganese through zinc, are electrosprayed, isolated in the ion trap and allowed to react with gases. The coordination number is ascertained by observing the reagent ligands that successfully react with the complex. It was generally observed that six‐coordinate complexes are unreactive, five‐coordinate complexes react with pyridine and ethylamine, four‐coordinate complexes react with pyridine, ethylamine and ammonia and threecoordinate complexes react with all the reagent ligands studied, including water and methanol. The order of reactivity for a given complex reacting with the various reagent ligands is found to follow the order of the electron‐donating ability of the reagent ligands. In addition, the effect of the metal center on the reactivity of the complexes in the gas phase is analogous to solution‐phase trends; electronic structure strongly influences the gas‐phase reactions. These results were then used to predict the complexation behavior of novel podand ligands for which condensed phase information is not available. The results indicate that ion–molecule chemistry in the gas phase may be useful in predicting the interactions between novel multidentate ligands and metals in solution. © 1998 John Wiley & Sons, Ltd.

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Gas phase reactions of the ion C₅H₅Fe⁺: A kinetic study

Cited by 14 publications

References 35 publications

Gas-phase ion–molecule reactions of divalent metal complex ions: Toward coordination structure analysis by mass spectrometry and some intrinsic coordination chemistry along the way

Gas-phase ion–molecule reactions of divalent metal complex ions: Toward coordination structure analysis by mass spectrometry and some intrinsic coordination chemistry along the way

The high-pressure segmented quadrupole collision cell (HP-SQCC) as an ion molecule reactor

Ion-molecule reactions in a quadrupole ion trap as a probe of the gas-phase structure of metal complexes

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