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

Gas-phase cyclometalation of [ArNi(PPh(3))(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. Copyright 2010 American Society for Mass Spectrometry. Published by Elsevier Inc. All rights reserved.