Cyanide–Arene Meisenheimer Complex Generated in Electrospray Ionization Mass Spectrometry Using Acetonitrile as a Solvent

  • Barbara Chiavarino
  • Philippe Maitre
  • Simonetta Fornarini
  • Maria Elisa Crestoni
Research Article


The C – C bond formation activated under negative electrospray ionization of an acetonitrile solution of 1,3,5-trinitrobenzene is reported. The solvent function is to provide a source of cyanide ion, a highly problematic reagent, which is found to attack the electron-deficient aromatic ring to form a covalently bound anionic complex (Meisenheimer complex). The structure of the complex is elucidated by means of collision induced dissociation mass spectrometry and IR multiple photon dissociation spectroscopy in the ‘fingerprint’ region.

Key words

IRMPD spectroscopy Meisenheimer complexes C – C coupling Tandem mass spectrometry Ab initio calculations 



The authors acknowledge funding for this work by the Italian MIUR (PRIN project no. 2009W2W4YF_004) and by the European Community’s Seventh Framework Programme (FP7/2007-2013, under grant agreement no 226716). The authors are grateful to J. M. Ortega, D. Scuderi, J. Lemaire, and to the CLIO team for their supportive assistance.

Dedicated to the memory of Professor Fulvio Cacace, mentor and friend, on the 10th anniversary of his untimely demise.

Supplementary material

13361_2013_703_MOESM1_ESM.pdf (52 kb)
ESM 1 (PDF 52 kb)


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Copyright information

© American Society for Mass Spectrometry 2013

Authors and Affiliations

  • Barbara Chiavarino
    • 1
  • Philippe Maitre
    • 2
  • Simonetta Fornarini
    • 1
  • Maria Elisa Crestoni
    • 1
  1. 1.Dipartimento di Chimica e Tecnologie del FarmacoUniversità degli Studi di Roma La SapienzaRomeItaly
  2. 2.Laboratoire de Chimie Physique, UMR8000 CNRS Faculté des SciencesUniversité Paris SudOrsay CedexFrance

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