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- W2168662821 abstract "The photoionization and dissociative photoionization of Im(iPr)2, 1,3-diisopropylimidazolin-2-ylidene, was investigated by imaging photoelectron photoion coincidence (iPEPICO) with vacuum ultraviolet (VUV) synchrotron radiation. A lone-pair electron of the carbene carbon atom is removed upon ionization and the molecular geometry changes significantly. Only 0.5 eV above the adiabatic ionization energy, IEad =7.52±0.1 eV, the carbene cation fragments, yielding propene or a methyl radical in parallel dissociation reactions with appearance energies of 8.22 and 8.17 eV, respectively. Both reaction channels appear at almost the same photon energy, suggesting a shared transition state. This is confirmed by calculations, which reveal the rate-determining step as hydrogen-atom migration from the isopropyl group to the carbene carbon center forming a resonance-stabilized imidazolium ion. Above 10.5 eV, analogous sequential dissociation channels open up. The first propene-loss fragment ion dissociates further and another methyl or propene is abstracted. Again, a resonance-stabilized imidazolium ion acts as intermediate. The aromaticity of the system is enhanced even in vertical ionization. Indeed, the coincidence technique confirms that a real imidazolium ion is produced by hydrogen transfer over a small barrier. The simple analysis of the breakdown diagram yields all the clues to disentangle the complex dissociative photoionization mechanism of this intermediate-sized molecule. Photoelectron photoion coincidence is a promising tool to unveil the fragmentation mechanism of larger molecules in mass spectrometry." @default.
- W2168662821 created "2016-06-24" @default.
- W2168662821 creator A5039777430 @default.
- W2168662821 creator A5061902310 @default.
- W2168662821 creator A5081265953 @default.
- W2168662821 creator A5081435208 @default.
- W2168662821 creator A5084014753 @default.
- W2168662821 date "2013-03-28" @default.
- W2168662821 modified "2023-09-24" @default.
- W2168662821 title "Unimolecular Reaction Mechanism of an Imidazolin-2-ylidene: An iPEPICO Study on the Complex Dissociation of an Arduengo-Type Carbene" @default.
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