Studies of gas-phase reactions of cationic iron complexes of 2-pyrimidinyloxy-N-arylbenzylamines by electrospray ionization tandem mass spectrometry |
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Authors: | Xu Chu Wang Hao-Yang Zhu Feng-Jun Guo Yin-Long Lu Long |
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Institution: | Shanghai Mass Spectrometry Center, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, PR China. |
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Abstract: | Electrospray ionization triple quadrupole mass spectrometry (ESI‐TSQ‐MS) and electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI‐FTICR‐MS) were used to investigate the interesting gas‐phase reactions of the cationic iron (Fe) complexes of 2‐pyrimidinyloxy‐N‐arylbenzylamines (1–6), which are generated by ESI when mixing their methanolic solutions. Further studies of these Fe complexes by collision‐induced dissociation (CID) show that Fe(III) complexes undergo an interesting gas‐phase single electron transfer (SET) reaction to give 1?+–6?+,with loss of neutral FeCl2, whereas Fe(II) can catalyze gas‐phase Smiles rearrangement reactions of compounds 1–6. By using different Fe(II)X2 salts (X = Cl or Br) with a set of reactants, the role of the counterion (X?) and the structure effect of the reactants on Fe(II)‐catalyzed gas‐phase Smiles rearrangement reactions are studied. Evidence obtained from by TSQ‐MS and FTICR‐MS experiments, hydrogen/deuterium (H/D) exchange experiments and theoretical computations supported some unique gas‐phase chemistries initiated by introduction of Fe(II) into 1. Importantly, by comparing the distinct gas‐phase reaction results of the cationic Fe(III) complexes with those of Fe(II) complexes, the charge state effects of iron on the gas‐phase chemistries of Fe complexes are revealed. Copyright © 2010 John Wiley & Sons, Ltd. |
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