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Gas-phase oxidation and reduction of some 1-(2-benzothiazolyl)-3,5-diphenyl formazans. Complex formation with transition metals under laser desorption ionization

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Journal of the American Society for Mass Spectrometry

Abstract

Five differently substituted 1-(2-benzothiazolyl)-3,5-diphenyl formazans were studied by laser desorption ionization (LDI) and matrix assisted laser desorption/ionization (MALDI) mass spectrometry. The best explanation of the results is that the formazan molecules are photoionized to molecular radical ions, which then further react by ion-molecule reactions. Supporting this proposal was the abundant formation of [M − H]+ ions under LDI. These ions are not observed at all under either electron or chemical ionization. Under MALDI, the extent of the oxidation process is clearly dependent on the ability of the matrix to act as a reducing agent. With transition metals the formazans formed singly charged 1:2 metal:formazan complexes. The most stable electronic configuration of the complex determined the oxidation state of the metal regardless of its initial oxidation state. In some cases, this process also demanded a gas-phase reduction of the formazan. The ionization efficiency and affinity for complex formation depended on the substituent at the 3-phenyl group; both were increased by an electron donating substituent. The formazans were also tested as potential matrices for MALDI. Reasonable results were observed for several groups of compounds; however, only the piperazine ligands produced higher quality spectra with formazans than with common commercial matrices.

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References

  1. Karas, M.; Hillenkamp, F. Anal. Chem. 1988, 60, 2299–2301.

    Article  CAS  Google Scholar 

  2. Tanaka, K.; Waki, H.; Ido, Y.; Akita, S.; Yoshida, Y.; Yoshida, T. Rapid Commun. Mass Spectrom. 1988, 2, 151–153.

    Article  CAS  Google Scholar 

  3. Beavis, R. C.; Chaudhary, T.; Chait, B. T. Org. Mass Spectrom. 1992, 27, 156–158.

    Article  CAS  Google Scholar 

  4. Beavis, R. C.; Chait, B. T. Rapid Commun. Mass Spectrom. 1989, 3, 432–435.

    Article  CAS  Google Scholar 

  5. Srupat, K.; Karas, M.; Hillemkamp, F. Int. J. Mass Spectrom. Ion Phys. 1991, 111, 89–102.

    Article  Google Scholar 

  6. Blais, J. C.; Tessier, M.; Bolbach, G.; Remaud, B.; Rozes, L.; Guittard, J.; Brunot, A.; Maréchal, E.; Tabet, J. C. Int. J. Mass Spectrom. Ion Processes 1995, 144, 131–138.

    Article  CAS  Google Scholar 

  7. Juhasz, P.; Costello, C. E.; Biemann, K. J. Am. Soc. Mass Spectrom. 1993, 4, 399–409.

    Article  CAS  Google Scholar 

  8. Juhasz, P.; Costello, C. E. Rapid Commun. Mass Spectrom. 1993, 7, 343–351.

    Article  CAS  Google Scholar 

  9. Ehring, H.; Karas, M.; Hillenkamp, F. Org. Mass Spectrom. 1992, 27, 472–480.

    Article  CAS  Google Scholar 

  10. Burton, R. D.; Watson, C. H.; Eyler, J. R.; Lang, G. L.; Powell, D. H.; Avery, M. Y. Rapid Commun. Mass Spectrom. 1997, 11, 443–446.

    Article  CAS  Google Scholar 

  11. Karas, M.; Bhar, U.; Strupat, K.; Hillenkamp, F.; Tsarbopoulos, A.; Pramanik, D. N. Anal. Chem. 1995, 67, 675–679.

    Article  CAS  Google Scholar 

  12. Gimon-Kinsel, M.; Preston-Schaffer, L. M.; Kinsel, G. R.; Russell, D. H. J. Am. Chem. Soc. 1997, 119, 2534–2540.

    Article  CAS  Google Scholar 

  13. Xu, N.; Huang, Z.-H.; Watson, J. T.; Gage, D. A. J. Am. Soc. Mass Spectrom. 1997, 8, 116–124.

    Article  CAS  Google Scholar 

  14. El’tsov, A. V.; Ol’khovikova, N. B.; Ponyaev, A. I.; Lipunova, G. N. Zh. Obshch. Khim. 1990, 60, 931–945.

    Google Scholar 

  15. El’tsov, A. V.; Yalandina, A. I.; Ponyaev, A. I.; Lipunova, G. N. Zh. Obshch. Khim. 1983, 53, 2587–2593.

    Google Scholar 

  16. El’tsov, A. V.; Yalandina, A. I.; Ponyaev, A. I. Zh. Org. Khim. 1982, 18, 1556–1557.

    Google Scholar 

  17. González, M. C.; San Román, E. J. Phys. Chem. 1989, 93, 3536–3540.

    Article  Google Scholar 

  18. Ratilainen, J.; Airola, K.; Kolehmainen, E.; Rissanen, K. Chem. Ber. 1997, 130, 1353–1359.

    Article  CAS  Google Scholar 

  19. Müller, A.; Bögge, H.; Diemann, E.; Brown, D.; O’Shea, S.; Lipunova, G. Naturwissenschaften 1994, 81, 136–137.

    Google Scholar 

  20. Kawamura, Y.; Ohya-Nishiguchi, H.; Yamauchi, J.; Deguchi, Y. Bull. Chem. Soc. Jpn. 1984, 57, 1441–1445.

    Article  CAS  Google Scholar 

  21. Price, R. J. Chem. Soc. 1971, 3385–3388.

  22. Kawamura, Y.; Yamauchi, J.; Ohya-Nishiguchi, H. Bull. Chem. Soc. Jpn. 1993, 66, 3593–3599.

    Article  CAS  Google Scholar 

  23. Garnovskii, A. D.; Bednyagina, N. P.; Kutznetsova, L. I.; Panyushkin, V. T.; Osipov, O. A.; Ogloblina, R. I.; Novikova, A. P. Russ. J. Inorg. Chem (Engl. Transl.) 1969, 14, 824–827.

    Google Scholar 

  24. El Ansary, A. L.; Hanna, Z. F. Egypt. J. Chem. 1989, 32, 393–403.

    Google Scholar 

  25. Price, R. J. Chem. Soc. 1971, 3379–3384.

  26. Mamyrin, B. A. Int. J. Mass Spectrom. Ion Processes 1994, 131, 1–19.

    Article  CAS  Google Scholar 

  27. Uchiumi, A.; Tanaka, H. Chromatographia 1989, 27, 622–624.

    Article  CAS  Google Scholar 

  28. Scott, F. L.; O’Sullivan, D. A.; Reilly, J. J. Am. Chem. Soc. 1953, 75, 5309–5312.

    Article  CAS  Google Scholar 

  29. Nuutinen, J. M. J.; Vainiotalo, P. Rapid Commun. Mass Spectrom. 1998, 12, 1691–1696.

    Article  CAS  Google Scholar 

  30. Jørgensen, T. J. D.; Bojesen, G.; Rahbek-Nielsen, H. Eur. Mass Spectrom. 1998, 4, 39–45.

    Article  Google Scholar 

  31. Lias, S. G.; Bartmess, J. E.; Liebman, J. F.; Holmes, J. L.; Levin, R. D.; Mallard, W. G. J. Phys. Chem. Ref. Data 1988, 17, Suppl. 1.

    Google Scholar 

  32. Lavanant, H.; Brunelle, A.; Hoppilliard, Y. Rapid Commun. Mass Spectrom. 1998, 12, 1137–1142.

    Article  CAS  Google Scholar 

  33. Yalcin, T.; Wang, J.; Wen, D.; Harrison, A. G. J. Am. Soc. Mass Spectrom. 1997, 8, 749–755.

    Article  CAS  Google Scholar 

  34. Xu, Y.; Zhang, X.; Yergey, A. J. Am. Soc. Mass Spectrom. 1995, 6, 25–29.

    Google Scholar 

  35. Cerda, B. A.; Wesdemiotis, C. J. Am. Chem. Soc. 1995, 117, 9734–9739.

    Article  CAS  Google Scholar 

  36. Nelson, R. W.; Hutchens, T. W. Rapid Commun. Mass Spectrom. 1992, 6, 4–8.

    Article  CAS  Google Scholar 

  37. Huheey, J. E. Inorganic Chemistry, Principles of Structure and Reactivity, 2nd ed.; Harper International Edition: New York, 1978; p 40.

    Google Scholar 

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Authors and Affiliations

  1. Department of Chemistry, University of Joensuu, P. O. Box 111, FIN-80101, Joensuu, Finland

    Jari M. J. Nuutinen, Ritva Romppanen, Silja Mäkinen & Pirjo Vainiotalo

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  1. Jari M. J. Nuutinen
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  2. Ritva Romppanen
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  3. Silja Mäkinen
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  4. Pirjo Vainiotalo
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Correspondence to Pirjo Vainiotalo.

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Nuutinen, J.M.J., Romppanen, R., Mäkinen, S. et al. Gas-phase oxidation and reduction of some 1-(2-benzothiazolyl)-3,5-diphenyl formazans. Complex formation with transition metals under laser desorption ionization. J Am Soc Mass Spectrom 10, 339–346 (1999). https://doi.org/10.1016/S1044-0305(98)00161-5

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  • DOI: https://doi.org/10.1016/S1044-0305(98)00161-5

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