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Issue 28, 2009
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Activation of X–H and X–D bonds (X = O, N, C) by alkaline-earth metal monoxide cations: experiment and theory

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Abstract

Experimental investigations are reported for reactions of MO˙+ (M = Ca, Sr, and Ba) with elemental hydrides water, ammonia and methane proceeding in the gas phase at 295 ± 3 K in helium buffer gas at a pressure of 0.35 ± 0.01 Torr. Measurements were taken with an inductively-coupled plasma/selected-ion flow tube (ICP/SIFT) tandem mass spectrometer and a novel electrospray ion source/ion selection quadrupole/selected-ion flow tube/triple quadrupole (ESI/qQ/SIFT/QqQ) mass spectrometer. All three alkaline-earth metal oxide ions exclusively abstract a H-atom from the three hydrides with rate coefficients > 1 × 10−11 cm3 molecule−1 s−1. Formation of metal hydroxide ion was followed by sequential addition of water or ammonia, but not methane. Density functional calculations have provided potential energy surfaces for the X–H bond activations leading to H-atom abstraction as well as those for O-atom transfer and H2O elimination (with ammonia and methane). A comparison of experimental and theoretical isotope effects points toward a mechanism involving the direct atom transfer from XH and XD to O in MO˙+via a three-centered transition structure.

Graphical abstract: Activation of X–H and X–D bonds (X = O, N, C) by alkaline-earth metal monoxide cations: experiment and theory

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Publication details

The article was received on 20 Feb 2009, accepted on 01 May 2009 and first published on 01 Jun 2009


Article type: Paper
DOI: 10.1039/B903413G
Citation: Phys. Chem. Chem. Phys., 2009,11, 5940-5951

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    Activation of X–H and X–D bonds (X = O, N, C) by alkaline-earth metal monoxide cations: experiment and theory

    A. Božović and D. K. Bohme, Phys. Chem. Chem. Phys., 2009, 11, 5940
    DOI: 10.1039/B903413G

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