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. © 2010 American Society for Mass Spectrometry.
Zhou, J., Zhao, Q., Chen, W. W., Wang, H., Lin, G. Q., Xu, M. H., & Guo, Y. (2010). Studies on gas-phase cyclometalations of [ArNi(PPh3)n]+ (n = 1 or 2) by electrospray ionization tandem mass spectrometry. Journal of the American Society for Mass Spectrometry, 21(7), 1265–1274. https://doi.org/10.1016/j.jasms.2010.03.040