Dissociation behavior of ionized valeramide

Loos, Jessica; Schröder, Detlef; Zummack, Waltraud; Schwarz, Helmut; Thissen, R.; Dutuit, O.

doi:10.1016/s1387-3806(01)00586-3

Cited by 43 publications

(20 citation statements)

References 33 publications

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“…[34][35][36] This effect can be understood by reference to the kinetic-energy spread of the incident beam.…”

Section: A C H T U N G T R E N N U N G (H 2 O)]mentioning

confidence: 99%

“…The ion-beam experiments themselves represent the integral kinetic energy distribution, which is simplified in Figure 6 c as the arithmetic average of the distributions in Figures 6 a and 6 b. When the resulting pattern in Figure 6 c is analyzed in terms of a kinetic modeling, the apparent rate constants show an increase with increasing progression of isotope exchange as indicated in the Figure. [ [34][35][36] The algebraic reason for this kinetically not meaningful order of rate constants is that the attempt to model the energy distributions sampled in the experiments with a single set of rate constants requires larger rate constants for the consecutive steps in order to cope for the increased amount of multiple exchange for the slow moving ions (see Figures 6 a versus 6 b). We note further that the increase of the relative rate by only a factor of two is a conservative estimate because thermal ion-molecule reactions often show rather steep negative energy dependence.…”

Section: A C H T U N G T R E N N U N G (H 2 O)]mentioning

confidence: 99%

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Micro‐Hydration of the MgNO₃⁺ Cation in the Gas Phase

et al. 2007

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Coordination complexes of the magnesium nitrate cation with water [MgNO(3)(H(2)O)(n)](+) up to n=7 are investigated by experiment and theory. The fragmentation patterns of [MgNO(3)(H(2)O)(n)](+) clusters generated via electrospray ionization indicate a considerable change in stability between n=3 and 4. Further, ion-molecule reactions of mass-selected [MgNO(3)(H(2)O)(n)](+) cations with D(2)O reveal the occurrence of consecutive replacement of water ligands by heavy water, and in this respect the complexes with n=4 and 5 are somewhat more reactive than their smaller homologs with n=1-3 as well as the larger clusters with n=6 and 7. For the latter two ions, the theory suggests the existence of isomers, such as complexes with monodentate nitrato ligands as well as solvent-separated ion pairs with a common solvation shell. The reactions observed and the ion thermochemistry are discussed in the context of ab initio calculations, which also reveal the structures of the various hydrated cation complexes.

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“…[34][35][36] This effect can be understood by reference to the kinetic-energy spread of the incident beam.…”

Section: A C H T U N G T R E N N U N G (H 2 O)]mentioning

confidence: 99%

Section: A C H T U N G T R E N N U N G (H 2 O)]mentioning

confidence: 99%

Micro‐Hydration of the MgNO₃⁺ Cation in the Gas Phase

et al. 2007

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“…Control experiments further confirm that the enol 2 +. , independently generated by the McLafferty rearrangement upon dissociative photoionization of valeramide,20 does not show such a threshold behavior; instead, “enol reactivity” is observed as soon as the ions are formed in the source 21…”

Section: Relative Stabilities (In Ev)[a] Of Neutral and Ionized Keto mentioning

confidence: 99%

Barrier Height Titration by Tunable Photoionization Combined with Chemical Monitoring: Unimolecular Keto/Enol Tautomerization of the Acetamide Cation Radical

Schröder

Thissen

Dutuit

et al. 2002

Angew. Chem. Int. Ed.

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By using a new “titration” technique, the activation barrier for the strictly unimolecular 1,3‐hydrogen migration 1.+→2.+ has been determined (0.74±0.06 eV; see reaction profile). With this technique the internal energy of 1.+ is controlled by variable photoionization of acetamide and the chemistry of the resulting enol ion 2.+ is then probed by structure‐specific ion–molecule reactions.

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“…and CD 3 . , respectively 50a,d. Although the inclusion of additional parameters will very often lead to improved fits, the operation of such a secondary KIE is directly supported by the experimental data in that CH 3 .…”

Section: Resultsmentioning

confidence: 96%

pH‐Triggered Dethreading–Rethreading and Switching of Cucurbit[6]uril on Bistable [3]Pseudorotaxanes and [3]Rotaxanes

Tuncel

Katterle

2008

Chemistry A European J

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The CH bond activation of small alkanes by the gaseous MgO+. cation is probed by mass spectrometric means. In addition to H‐atom abstraction from methane, the MgO+. cation reacts with ethane, propane, n‐ and iso‐butane through several pathways, which can all be assigned to the occurrence of initial CH bond activations. Specifically, the formal CC bond cleavages observed are assigned to CH bond activation as the first step, followed by cleavage of a β‐CC bond concomitant with release of the corresponding alkyl radical. Kinetic modeling of the observed product distributions reveals a high preference of MgO+. for the attack of primary CH bonds. This feature represents a notable distinction of the main‐group metal oxide MgO+. from various transition‐metal oxide cations, which show a clear preference for the attack of secondary CH bonds. The results of complementary theoretical calculations indicate that the CH bond activation of larger alkanes by the MgO+. cation is subject to pronounced kinetic control.

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Dissociation behavior of ionized valeramide

Cited by 43 publications

References 33 publications

Micro‐Hydration of the MgNO₃⁺ Cation in the Gas Phase

Micro‐Hydration of the MgNO₃⁺ Cation in the Gas Phase

Barrier Height Titration by Tunable Photoionization Combined with Chemical Monitoring: Unimolecular Keto/Enol Tautomerization of the Acetamide Cation Radical

pH‐Triggered Dethreading–Rethreading and Switching of Cucurbit[6]uril on Bistable [3]Pseudorotaxanes and [3]Rotaxanes

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Dissociation behavior of ionized valeramide

Cited by 43 publications

References 33 publications

Micro‐Hydration of the MgNO3+ Cation in the Gas Phase

Micro‐Hydration of the MgNO3+ Cation in the Gas Phase

Barrier Height Titration by Tunable Photoionization Combined with Chemical Monitoring: Unimolecular Keto/Enol Tautomerization of the Acetamide Cation Radical

pH‐Triggered Dethreading–Rethreading and Switching of Cucurbit[6]uril on Bistable [3]Pseudorotaxanes and [3]Rotaxanes

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Micro‐Hydration of the MgNO₃⁺ Cation in the Gas Phase

Micro‐Hydration of the MgNO₃⁺ Cation in the Gas Phase