Abstract
Two novel monofunctionalized fulleropyrrolidine derivatives (Prato adducts) were prepared and characterized by matrix-assisted laser desorption/ionization (MALDI) and electrospray ionization (ESI). MALDI experiments conducted in the positive-ion mode on pure and mixed samples of both monofunctionalized fullerene derivatives revealed the efficient formation of bisadducts (in the case of the pure samples) and mixed bisadducts (in the case of a mixed sample). Bisadducts were not observed in the ESI experiments and thus not present in the sample. A mechanism for the MALDI formation of these bisadduct ions is proposed in which an azomethine ylide fragment is formed in situ from the monofunctionalized fulleropyrrolidine species upon laser irradiation. This fragment, which can survive as an intact moiety in the gas phase in the special environment provided by the MALDI experiment, is then able to attach to a fulleropyrrolidine monoadduct which acts as a dipolarophile, thus leading to the formation of a bisadduct fullerene derivative. The unprecedented re-attachment of the azomethine ylide implies that the establishment of the ligand attainment of Prato adducts based on MALDI analysis alone can lead to wrong assignments.
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Acknowledgments
The authors thank Maite Alonso Pascual and Mª Jesus Vicente Arana from the SIdI of the Universidad Autónoma de Madrid, Spain, for recording some of the mass spectra. Support is acknowledged from the Spanish MICINN (CTQ2011-24187/BQU and CONSOLIDER INGENIO 2010, CSD2007-00010 on Molecular Nanoscience) and the CAM (MADRISOLAR-2, S2009/PPQ/ 1533). The authors thank the German Science Foundation (DFG)–SFB 953 Synthetic Carbon Allotropes–for their financial support.
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Bottari, G., Dammann, C., Torres, T. et al. Laser-Induced Azomethine Ylide Formation and Its Covalent Entrapment by Fulleropyrrolidine Derivatives During MALDI Analysis. J. Am. Soc. Mass Spectrom. 24, 1413–1419 (2013). https://doi.org/10.1007/s13361-013-0680-3
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DOI: https://doi.org/10.1007/s13361-013-0680-3