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

Abstract

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 

Notes

Acknowledgments

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)

References

  1. 1.
    Anbarasan, P., Schareina, T., Beller, M.: Recent developments and perspectives in palladium-catalyzed cyanation of aryl halides: synthesis of benzonitriles. Chem. Soc. Rev. 40, 5049–5067 (2011)CrossRefGoogle Scholar
  2. 2.
    Zhang, G.-Y., Yu, J.-T., Hu, M.-L., Cheng, J.: Palladium-catalyzed cyanation of aryl halides with CuSCN. J. Org. Chem. 78, 2710–2714 (2013)CrossRefGoogle Scholar
  3. 3.
    Zheng, S., Yu, C., Shen, Z.: Ethyl cyanoacetate: a new cyanating agent for the palladium-catalyzed cyanation of aryl halides. Org. Lett. 14, 3644–3647 (2012)CrossRefGoogle Scholar
  4. 4.
    Yeung, P.Y., Tsang, C.P., Kwong, F.Y.: Efficient cyanation of aryl bromides with K4[Fe(CN)6] catalyzed by a palladium-indolylphosphine complex. Tetrahedron Lett. 52, 7038–7041 (2011)CrossRefGoogle Scholar
  5. 5.
    Wen, Q., Jin, J., Hu, B., Lu, P., Wang, Y.: Palladium-catalyzed cyanide metathesis: utilization of benzyl cyanide as an operator-benign reagent for aryl halide cyanations. RSC Adv. 2, 6167–6169 (2012)CrossRefGoogle Scholar
  6. 6.
    Kim, J., Kim, H.J., Chang, S.: Synthesis of aromatic nitriles using nonmetallic cyano-group sources. Angew. Chem. Int. Ed. 51, 11948–11959 (2012)CrossRefGoogle Scholar
  7. 7.
    Chiavarino, B., Crestoni, M.E., Fornarini, S., Lanucara, F., Lemaire, J., Maitre, P.: Meisenheimer complexes positively characterized as stable intermediates in the gas phase. Angew. Chem. Int. Ed. 46, 1995–1998 (2007)CrossRefGoogle Scholar
  8. 8.
    Chiavarino, B., Crestoni, M.E., Fornarini, S., Lanucara, F., Lemaire, J., Maitre, P., Scuderi, D.: Molecular complexes of simple anions with electron-deficient arenes: spectroscopic evidence for two types of structural motifs for anion-arene interactions. Chem. Eur. J. 15, 8185–8195 (2009)CrossRefGoogle Scholar
  9. 9.
    Oomens, J., Sartakov, B.G., Meijer, G., von Helden, G.: Gas-phase infrared multiple photon dissociation spectroscopy of mass-selected molecular ions. Int. J. Mass Spectrom. 254, 1–19 (2006)CrossRefGoogle Scholar
  10. 10.
    MacAleese, L., Maitre, P.: Infrared spectroscopy of organometallic ions in the gas phase: from model to real world complexes. Mass Spectrom. Rev. 26, 583–605 (2007)CrossRefGoogle Scholar
  11. 11.
    Eyler, J.R.: Infrared multiple photon dissociation spectroscopy of ions in Penning traps. Mass Spectrom. Rev. 28, 448–467 (2009)CrossRefGoogle Scholar
  12. 12.
    Fridgen, T.D.: Infrared consequence spectroscopy of gaseous protonated and metal ion cationized complexes. Mass Spectrom. Rev. 28, 586–607 (2009)CrossRefGoogle Scholar
  13. 13.
    Polfer, N.C.: Infrared multiple photon dissociation spectroscopy of trapped ions. Chem. Soc. Rev. 40, 2211–2221 (2011)CrossRefGoogle Scholar
  14. 14.
    Duncan, M.A.: Infrared laser spectroscopy of mass-selected carbocations. J. Phys. Chem. A 116, 11477–11491 (2012)CrossRefGoogle Scholar
  15. 15.
    Roithova, J.: Characterization of reaction intermediates by ion spectroscopy. Chem. Soc. Rev. 41, 547–559 (2012)CrossRefGoogle Scholar
  16. 16.
    MacAleese, L., Simon, A., McMahon, T.B., Ortega, J.-M., Scuderi, D., Lemaire, J., Maitre, P.: Mid-IR spectroscopy of protonated leucine methyl ester performed with an FTICR or a Paul type ion-trap. Int. J. Mass Spectrom. 249/250, 14–20 (2006)CrossRefGoogle Scholar
  17. 17.
    Chiavarino, B., Crestoni, M.E., Fornarini, S., Lanucara, F., Lemaire, J., Maitre, P., Scuderi, D.: Infrared spectroscopy of isolated nucleotides. 1. The cyclic 3′,5′-adenosine monophosphate anion. Int. J. Mass Spectrom. 270, 111–117 (2008)CrossRefGoogle Scholar
  18. 18.
    Chiavarino, B., Crestoni, M.E., Fornarini, S., Taioli, S., Mancini, I., Tosi, P.: Infrared spectroscopy of copper-resveratrol complexes: a joint experimental and theoretical study. J. Chem. Phys. 37(2), 024301–024309 (2012)Google Scholar
  19. 19.
    Lanucara, F., Chiavarino, B., Crestoni, M.E., Scuderi, D., Sinha, R.K., Maitre, P., Fornarini, S.: Naked five-coordinate FeIII(NO) porphyrin complexes: vibrational and reactivity features. Inorg. Chem. 50, 4445–4452 (2011)CrossRefGoogle Scholar
  20. 20.
    Chiavarino, B., Crestoni, M.E., Fornarini, S., Dopfer, O., Lemaire, J., Maitre, P.: IR spectroscopic features of gaseous C7H7O+ ions: benzylium versus tropylium ion structures. J. Phys. Chem. A 110, 9352–9360 (2006)CrossRefGoogle Scholar
  21. 21.
    Chiavarino, B., Crestoni, M.E., Fornarini, S., Lemaire, J., Maitre, P., MacAleese, L.: π-complex structure of gaseous benzene-NO cations assayed by IR multiple photon dissociation spectroscopy. J. Am. Chem. Soc. 128, 12553–12561 (2006)CrossRefGoogle Scholar
  22. 22.
    Lorenz, U.J., Lemaire, J., Maitre, P., Crestoni, M.-E., Fornarini, S., Dopfer, O.: Protonation of heterocyclic aromatic molecules: IR signature of the protonation site of furan and pyrrole. Int. J. Mass Spectrom. 267, 43–53 (2007)CrossRefGoogle Scholar
  23. 23.
    Simon, A., MacAleese, L., Maitre, P., Lemaire, J., McMahon, T.B.: Fingerprint vibrational spectra of protonated methyl esters of amino acids in the gas phase. J. Am. Chem. Soc. 129, 2829–2840 (2007)CrossRefGoogle Scholar
  24. 24.
    Sinha, R.K., Chiavarino, B., Fornarini, S., Lemaire, J., Maitre, P., Crestoni, M.E.: Protonated sulfuric acid: vibrational signatures of the naked ion in the near- and mid-IR. J. Phys. Chem. Lett. 1, 1721–1724 (2010)CrossRefGoogle Scholar
  25. 25.
    Moore, D.T., Oomens, J., Eyler, J.R., von, H.G., Meijer, G., Dunbar, R.C.: Infrared spectroscopy of gas-phase Cr+ coordination complexes: determination of binding sites and electronic states. J. Am. Chem. Soc. 127, 7243–7254 (2005)Google Scholar
  26. 26.
    Schroeder, D., Schwarz, H., Milko, P., Roithova, J.: Dissociation routes of protonated toluene probed by infrared spectroscopy in the gas phase. J. Phys. Chem. A 110, 8346–8353 (2006)CrossRefGoogle Scholar
  27. 27.
    Chiavarino, B., Crestoni, M.E., Fornarini, S., Lemaire, J., MacAleese, L., Maitre, P.: Infrared spectroscopy of protonated phenylsilane in the gas phase. Chem. Phys. Chem. 6, 437–440 (2005)CrossRefGoogle Scholar
  28. 28.
    Chiavarino, B., Crestoni, M.E., Dopfer, O., Maitre, P., Fornarini, S.: Benzylium versus tropylium ion dichotomy: vibrational spectroscopy of gaseous C8H9 + ions. Angew. Chem. Int. Ed. 51, 4947–4949 (2012)CrossRefGoogle Scholar
  29. 29.
    Chiavarino, B., Crestoni, M.E., Fornarini, S., Scuderi, D., Salpin, J.-Y.: interaction of cisplatin with adenine and guanine: a combined irmpd, MS/MS, and Theoretical Study. J. Am. Chem. Soc. 135, 1445–1455 (2013)CrossRefGoogle Scholar
  30. 30.
    Hay, B.P., Bryantsev, V.S.: Anion-arene adducts: C–H hydrogen bonding, anion-π interaction, and carbon bonding motifs. Chem. Commun. 2417–2428 (2008)Google Scholar
  31. 31.
    Mueller, T., Badu-Tawiah, A., Cooks, R.G.: Accelerated carbon[n.63743]Carbon bond-forming reactions in preparative electrospray. Angew. Chem. Int. Ed. 51, 11832–11835 (2012)CrossRefGoogle Scholar
  32. 32.
    Kebarle, P., Verkerk, U.H.: Electrospray: from ions in solution to ions in the gas phase, what we know now. Mass Spectrom. Rev. 28, 898–917 (2009)CrossRefGoogle Scholar
  33. 33.
    Song, Y., Cooks, R.G.: Atmospheric pressure ion/molecule reactions for the selective detection of nitroaromatic explosive using acetonitrile and air as reagents. Rapid Commun. Mass Spectrom. 20, 3130–3138 (2006)CrossRefGoogle Scholar
  34. 34.
    Dillow, G.W., Kebarle, P.: Fluoride affinities of perfluorobenzenes C6F5X. Meisenheimer complexes in the gas phase and solution. J. Am. Chem. Soc. 110, 4877–4882 (1988)CrossRefGoogle Scholar
  35. 35.
    Chen, H., Chen, H., Cooks, R.G.: Meisenheimer complexes bonded at carbon and at oxygen. J. Am. Soc. Mass Spectrom. 15, 998–1004 (2004)CrossRefGoogle Scholar
  36. 36.
    Giroldo, T., Xavier, L.A., Riveros, J.M.: An unusually fast nucleophilic aromatic displacement reaction: the gas-phase reaction of fluoride ions with nitrobenzene. Angew. Chem. Int. Ed. 43, 3588–3590 (2004)CrossRefGoogle Scholar
  37. 37.
    Fernandez, I., Frenking, G., Uggerud, E.: Rate-determining factors in nucleophilic aromatic substitution reactions. J. Org. Chem. 75, 2971–2980 (2010)CrossRefGoogle Scholar
  38. 38.
    Garver, J.M., Yang, Z., Kato, S., Wren, S.W., Vogelhuber, K.M., Lineberger, W.C., Bierbaum, V.M.: Gas phase reactions of 1,3,5-triazine: proton transfer, hydride transfer, and anionic σ-adduct formation. J. Am. Soc. Mass Spectrom. 22, 1260–1272 (2011)CrossRefGoogle Scholar
  39. 39.
    Danikiewicz, W., Bienkowski, T., Poddebniak, D.: Generation and reactions of anionic σ-adducts of 1,3-dinitrobenzene and 1,3,5-trinitrobenzene with carbanions in a gas phase, using an electrospray ion source as the chemical reactor. J. Am. Soc. Mass Spectrom. 15, 927–933 (2004)CrossRefGoogle Scholar
  40. 40.
    Danikiewicz, W., Bienkowski, T., Wojciechowski, K.: Application of electrospray ionization mass spectrometry for studies of anionic σ-adducts of aromatic nitro-compounds. Tetrahedron Lett. 45, 931–934 (2004)CrossRefGoogle Scholar

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

Personalised recommendations