Abstract
1,n-Alkanediammonium cations in noncovalent complexes with two dibenzo-18-crown-6-ether (DBCE) ligands undergo an unusual intramolecular tandem hydrogen atom and proton transfer to the crown ether ligand upon charge reduction by electron capture. Deuterium labeling established that both migrating hydrogens originated from the ammonium groups. The double hydrogen transfer was found to depend on the length of the alkane chain connecting the ammonium groups. Ab initio calculations provided structures for select alkanediammonium·dibenzo-18-crown-6-ether complexes and dissociation products. This first observation of an intra-complex hydrogen transfer is explained by the unusual electronic properties of the complexes and the substantial hydrogen atom affinity of the aromatic rings in the crown ligand.
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Dearden, D. V.; Chu, I.-H. Relative Ammonium Ion Affinities of 18-Crown-6 and the Isomers of Dicyclohexano-18-Crown-6. J. Inclusion Phenom. Mol. Recogn. Chem. 1997, 29, 269–282.
Liang, Y.; Bradshaw, J. S.; Dearden, D. V. The Thermodynamic Basis for Enantiodiscrimination: Gas-Phase Measurement of the Enthalpy and Entropy of Chiral Amine Recognition by Dimethyldiketopyridino-18-Crown-6. J. Phys. Chem. A. 2002, 106, 9665–9671.
Wilson, J. J.; Kirkovits, G. J.; Sessler, J. L.; Brodbelt, J. S. Photodissociation of Noncovalent Peptide-Crown Ether Complexes. J. Am. Soc. Mass Spectrom. 2008, 19, 257–260.
Kellersberger, K. A.; Anderson, J. D.; Ward, S. M.; Krakowiak, K. E.; Dearden, D. V. Encapsulation of N2, O2, Methanol, or Acetonitrile by Decamethylcucurbit[5]uril(NH4+)2 Complexes in the Gas Phase: Influence of the Guest on “Lid” Tightness. J. Am. Chem. Soc. 2001, 123, 11316–11317.
Zhang, H.; Paulsen, E. S.; Walker, K. A.; Krakowiak, K. E.; Dearden, D. V. Cucurbit[6]uril Pseudorotaxanes: Distinctive Gas-Phase Dissociation and Reactivity. J. Am. Chem. Soc. 2003, 125, 9284–9285.
Osaka, I.; Kondou, M.; Selvapalam, N.; Samal, S.; Kim, K.; Rekharsky, M. V.; Inoue, Y.; Arakawa, R. Characterization of Host—Guest Complexes of Cucurbit[n]uril (n = 6, 7) by Electrospray Ionization Mass Spectrometry. J. Mass Spectrom. 2006, 41, 202–207.
Zhang, H.; Ferrell, T. A.; Asplund, M. C.; Dearden, D. V. Molecular Beads on a Charged Molecular String: α, ω-Alkyldiammonium Complexes of Cucurbit[6]uril in the Gas Phase. Int. J. Mass Spectrom. 2007, 265, 187–196.
Ling, Y.; Mague, J. T.; Kaifer, A. E. Inclusion Complexation of Diquat and Paraquat by the Hosts Cucurbit[7]uril and Cucurbit[8]uril. Chem. Eur. J. 2007, 13, 7908–7914.
Stone, M. M.; Franz, A. H.; Lebrilla, C. B. Noncovalent Calixarene—Amino Acid Complexes Formed by MALDI-MS. J. Am. Soc. Mass Spectrom. 2002, 13, 964–974.
Arai, S.; Ishihara, S.; Takeoka, S.; Ohkawa, H.; Shibue, T.; Nishide, H. Stability of Porphyrin—calix[4]arene Complexes Analyzed by Electrospray Ionization Mass Spectrometry. Rapid Commun. Mass Spectrom. 2004, 18, 2065–2068.
Rozhenko, A. B.; Schoeller, W. W.; Letzel, M. C.; Decker, B.; Agena, C.; Mattay, J. Calixarenes as Hosts for Ammonium Cations: A Quantum Chemical Study and Mass Spectrometric Investigations. Chem. Eur. J. 2006, 12, 8995–9000.
Da Silva, E.; Rousseau, C. F.; Zanella-Cleon, I.; Becchi, M.; Coleman, A. W. Mass Spectrometric Determination of Association Constants of Bovine Serum Albumin (BSA) with para-Sulfonato-Calix[n]arene Derivatives. J. Inclusion Phenom. Macrocycl. Chem. 2006, 54, 53–59.
Kellersberger, K. A.; Dejsupa, C.; Liang, Y.; Pope, R. M.; Dearden, D. V. Gas Phase Studies of Ammonium-Cyclodextrin Compounds Using Fourier Transform Ion Cyclotron Resonance. Int. J. Mass Spectrom. 1999, 193, 181–195.
Garcia, B.; Ramirez, J.; Wong, S.; Lebrilla, C. B. Thermal Dissociation of Protonated Cyclodextrin-Amino Acid Complexes in the Gas Phase. Int. J. Mass Spectrom. 2001, 210/211, 215–222.
Lebrilla, C. B. The Gas-Phase Chemistry of Cyclodextrin Inclusion Complexes. Acc. Chem. Res. 2001, 34, 653–661.
Vrkic, A. K.; O’Hair, R. A. J.; Lebrilla, C. B. Unusual Covalent Bond-Breaking Reactions of β-Cyclodextrin Inclusion Complexes of Nucleobases/Nucleosides and Related Guest Molecules. Eur. J. Mass Spectrom. 2003, 9, 563–577.
Guo, M.; Song, F.; Liu, Z.; Liu, S. Characterization of Noncovalent Complexes of Rutin with Cyclodextrins by Electrospray Ionization Tandem Mass Spectrometry. J. Mass Spectrom. 2004, 39, 594–599.
Wen, X.; Liu, Z.; Zhu, T. Mass Spectrometry and Molecular Modeling Studies on the Inclusion Complexes Between α-, β-Cyclodextrins and Simvastatin. Chem. Phys. Lett. 2005, 405, 114–117.
Ahn, S.; Cong, X.; Lebrilla, C. B.; Gronert, S. Zwitterion Formation in Gas-Phase Cyclodextrin Complexes. J. Am. Soc. Mass Spectrom. 2005, 16, 166–175.
Li, H.; Zhou, J.; Tang, F.; Yuan, G. Investigation of Noncovalent Complexes Between β-Cyclodextrin and Polyamide Acids Containing N-Methylpyrrole and N-Methylimidazole by Electrospray Ionization Mass Spectrometry. J. Am. Soc. Mass Spectrom. 2006, 17, 9–14.
Zhang, H.; Chen, G.; Wang, L.; Ding, L.; Tian, Y.; Jin, W.; Zhang, H. Study on the Inclusion Complexes of Cyclodextrin and Sulphonated azo Dyes by Electrospray Ionization Mass Spectrometry. Int. J. Mass Spectrom. 2006, 252, 1–10.
Zhang, M.; Shi, Z.; Bai, Y.; Gao, Y.; Hu, R.; Zhao, F. Using Molecular Recognition of β-Cyclodextrin to Determine Molecular Weights of Low-Molecular-Weight Explosives by MALDI-TOF Mass Spectrometry. J. Am. Soc. Mass Spectrom. 2006, 17, 189–193.
Greisch, J.-F.; Kyritsoglou, S.; Leyh, B.; De Pauw, E. Mass spectrometric study of the ionized C60: (γ-Cyclodextrin)2 Inclusion Complex by Collision Induced Dissociation. J. Mass Spectrom. 2008, 43, 242–250.
Schug, K.; Lindner, W. Development of a Screening Technique for Noncovalent Complex Formation Between Guanidinium- and Phosphonate-Functionalized Amino Acids by Electrospray Ionization Ion Trap Mass Spectrometry: Assessing Ionization and Functional Group Interaction. Int. J. Mass Spectrom. 2004, 235, 213–222.
Beyeh, N. K.; Feher, D.; Luostarinen, M.; Schalley, C. A.; Rissanen, K. Synthesis of Chiral Resorcinarene-Based Hosts and a Mass Spectrometric Study of Their Chemistry in Solution and the Gas Phase. J. Inclusion Phenom. Macrocycl. Chem. 2006, 56, 381–394.
Liebig, T.; Luening, U.; Grotemeyer, J. Supramolecular Clusters Between Carbohydrates and Concave Pyridines: Detection in the Gas Phase by Resonance-Enhanced Multiphoton Ionization Reflectron Time-of-Flight Mass Spectrometry. Eur. J. Mass Spectrom. 2006, 12, 117–120.
Makinen, M.; Kalenius, E.; Neitola, R.; Rissanen, K.; Vainiotalo, P. The Complex Formation of Tetracyclohexylammonium C1-Resorcinarene with Various Guests—an Electrospray Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry study. Rapid Commun. Mass Spectrom. 2008, 22, 1377–1383.
Di Tullio, A.; Reale, S.; De Angelis, F. Molecular Recognition by Mass Spectrometry. J. Mass Spectrom. 2005, 40, 845–865.
Cong, X.; Czerwieniec, G.; McJimpsey, E.; Ahn, S.; Troy, F. A.; Lebrilla, C. B. Structural Relationships in Small Molecule Interactions Governing Gas-Phase Enantioselectivity and Zwitterionic Formation. J. Am. Soc. Mass Spectrom. 2006, 17, 442–452.
Weimann, D. P.; Schalley, C. A. Host—Guest Chemistry of Self-Assembling Supramolecular Capsules in the Gas Phase. Supramol. Chem. 2008, 20, 117–128.
Sherman, C. L.; Brodbelt, J. S. Partitioning Model for Competitive Host—Guest Complexation in ESI-MS. Anal. Chem. 2005, 77, 2512–2523.
Grigorean, G.; Gronert, S.; Lebrilla, C. B. Enantioselective Gas-Phase Ion-Molecule Reactions in a Quadrupole Ion Trap. Int. J. Mass Spectrom. 2002, 219, 79–87.
Grigorean, G.; Cong, X.; Lebrilla, C. B. Chiral Analyses of Peptides by Ion/Molecule Reactions. Int. J. Mass Spectrom. 2004, 234, 71–77.
Chakraborty, T.; Holm, A. I. S.; Hvelplund, P.; Nielsen, S. B.; Poully, J.-C.; Worm, E. S.; Williams, E. R. On the Survival of Peptide Cations After Electron Capture: Role of Internal Hydrogen Bonding and Microsolvation. J. Am. Soc. Mass Spectrom. 2006, 17, 1675–1680.
Holm, A. I. S.; Larsen, M. K.; Panja, S.; Hvelplund, P.; Nielsen, S. B.; Leib, R. D.; Donald, W. A.; Williams, E. R.; Hao, C.; Tureček, F. Electron capture, femtosecond electron transfer and theory: A study of noncovalent crown ether 1,n-diammonium alkane complexes. Int. J. Mass Spectrom. 2008, 276, 116–126.
Zubarev, R. A.; Kelleher, N. L.; McLafferty, F. W. Electron Capture Dissociation of Multiply Charged Protein Cations: A Nonergodic Process. J. Am. Chem. Soc. 1998, 120, 3265–3266.
Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery, J. A. Jr.,; Vreven, T.; Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austn, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; Pople, J. A. Gaussian 03, Revision B 05; Gaussian, Inc.: Pittsburgh, PA, 2003.
Becke, A. D. A New Mixing of Hartree-Fock and Local Density-Functional Theories. J. Chem. Phys. 1993, 98, 1372–1377.
Becke, A. D. Density Functional Thermochemistry. III. The Role of Exact Exchange. J. Chem. Phys. 1993, 98, 5648–5652.
Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F.; Frisch, M. J. Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields. J. Phys. Chem. 1994, 98, 11623–11627.
Rauhut, G.; Pulay, P. Transferable Scaling factors for Density Functional Derived Vibrational Force Fields. J. Phys. Chem. 1995, 99, 3093–3100.
[caron]Cížek, J.; Paldus, J.; Šroubková, L. Cluster Expansion Analysis for Delocalized Systems. Int. J. Quantum. Chem. 1969, 3, 149–167.
Purvis, G. D. III; Bartlett, R. J. A Full Coupled-Cluster Singles and Doubles model: The Inclusion of Disconnected Triples. J. Chem. Phys. 1982, 76, 1910–1918.
Curtiss, L. A.; Raghavachari, K.; Pople, J. A. Gaussian-2 Theory Using Reduced Møller-Plesset Orders. J. Chem. Phys. 1993, 98, 1293–1298.
Stratmann, R. E.; Scuseria, G. E.; Frisch, M. J. An Efficient Implementation of Time-Dependent Density Functional Theory for the Calculation of Excitation Energies of Large Molecules. J. Chem. Phys. 1998, 109, 8218–8224.
Reed, A. E.; Weinstock, R. B.; Weinhold, F. Natural Population Analysis. J. Chem. Phys. 1985, 83, 735–745.
Tureček, F.; Chen, X.; Hao, C. Where Does the Electron Go?: Electron Distribution and Reactivity of Peptide Cation-Radicals Formed by Electron Transfer in the Gas Phase. J. Am. Chem. Soc. 2008, 130, 8818–8833.
Rogers, R. D.; Kurihara, L. K.; Benning, M. M. F-Element/Crown Ether Complexes. 10: Oxidation of Uranium Tetrachloride to Tetrachlorodioxouranate(2-) in the Presence of Crown Ethers: Structural Characterization of Crown Ether Complexed Ammonium Ions. Inorg. Chem. 1987, 26, 4346–4352.
Dapporto, P.; Paoli, P.; Matijasic, I.; Tusek-Bozic, L. Crystal Structures of Complexes of Ammonium and Potassium Hexafluorophosphate with Dibenzo-18-Crown-6: Molecular Mechanics Studies on the Uncomplexed Macrocycle. Inorg. Chim. Acta. 1996, 252, 383–389.
NIST Standard Reference Database Number 69; March, 2003 Release; http://webbook.nist.gov/chemistry.
Chung, T. W.; Tureček, F. Selecting Fixed-Charge Groups for Electron-Based Peptide Dissociations: A Computational Study of Pyridinium Tags. Int. J. Mass Spectrom. 2008, 276, 127–135.
Yao, C.; Tureček, F. Hypervalent Ammonium Radicals: Competitive N—C and N—H Bond Dissociations in Methylammonium and Ethylammonium. Phys. Chem. Chem. Phys. 2005, 7, 912–920.
Syrstad, E. A.; Tureček, F. Toward a General Mechanism of Electron-Capture Dissociation. J. Am. Soc. Mass Spectrom. 2005, 16, 208–224.
Sobczyk, M.; Anusiewicz, I.; Berdys-Kochanska, J.; Sawicka, A.; Skurski, P.; Simons, J. Coulomb-Assisted Dissociative Electron Attachment: Application to a Model Peptide. J. Phys. Chem. A. 2005, 109, 250–258.
Longevialle, P.; Botter, R. Electron Impact Mass Spectra of Bifunctional Steroids: The Interaction Between Ionic and Neutral Fragments Derived from the Same Parent Ion. Org. Mass Spectrom. 1983, 18, 1–8.
Longevialle, P.; Bouchoux, G.; Hoppilliard, Y. Interaction of Remote Functional Groups (Amide and Amine) in Steroidal Compounds After Electron Ionization. Org. Mass Spectrom. 1990, 25, 527–536.
Longevialle, P. Ion-Neutral Complexes in the Unimolecular Reactivity of Organic Cations in the Gas Phase. Mass Spectrom. Rev. 1992, 11, 157–192.
Longevialle, P.; Lefevre, O. The Role of Ion-Neutral Reorientation in the Unimolecular Reactivity of Metastable Electron-Ionized Amines: Completing Influences of the Size of the Fragments and the Polarity of the Neutral. Rapid Commun. Mass Spectrom. 1996, 10, 621–626.
Morton, T. H. Gas Phase Analogs of Solvolysis Reactions. Tetrahedron. 1982, 38, 3195–3243.
Morton, T. H. The Reorientation Criterion and Positive Ion-Neutral Complexes. Org. Mass Spectrom. 1992, 27, 353–368.
Bondi, A. van der Waals Volumes and Radii. J. Phys. Chem. 1964, 68, 441–451.
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Published online December 9, 2008
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Hao, C., Tureček, F. Host-guest hydrogen atom transfer induced by electron capture. J Am Soc Mass Spectrom 20, 639–651 (2009). https://doi.org/10.1016/j.jasms.2008.12.001
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DOI: https://doi.org/10.1016/j.jasms.2008.12.001