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Studies on gas-phase cyclometalations of [ArNi(PPh3)n]+ (n = 1 or 2) by electrospray ionization tandem mass spectrometry

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Abstract

Gas-phase cyclometalation of [ArNi(PPh3)n]+ (n = 1, 2) complexes have been studied by ESI-MS/MS. The electron-donating substituents of aromatic iodides in the para position were found to inhibit the cyclometalation process of losing ArH, while the electron-withdrawing substituents in the para position were found to enhance it. These results indicate that the cyclometalation process of losing ArH is favored by electron-deficient aromatic groups. In addition, the detailed dissociation pathways of the cationic nickel complexes were studied, and among these pathways, the process of aryl-aryl interchange was also found to proceed in ESI-MS/MS.

Keywords

Fragmentation Pathway Electrospray Mass Spectrometry Reductive Elimination Nickel Isotope Aromatic Iodide 
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© American Society for Mass Spectrometry 2010

Authors and Affiliations

  1. 1.Shanghai Mass Spectrometry Center, Shanghai Institute of Organic ChemistryChinese Academy of SciencesShanghaiChina
  2. 2.CAS Key Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic ChemistryChinese Academy of SciencesShanghaiChina

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