[en] The gas-phase reactivities of the well-known (.)CH(2)CH(2)C(+)=O and (.)CH(2)CH(2)CH(2)C(+)=O distonic ions towards neutral pyridine were studied both experimentally (six sector hybrid mass spectrometer) and theoretically (density functional theory and Mø
K.M. Stirk, M.L.K. Kiminkinen and H.I. Kenttämaa, "Ion-molecule reactions of distonic radical cations", Chem. Rev. 92, 1649-1665 (1992).
(a) B.F. Yates, W.J. Bouma and L. Radom, "Detection of the prototype phosphonium (CH2PH3), sulfonium (CH 2SH2), and chloronium (CH2ClH) Ylides by neutralization-reionization mass spectrometry: a theoretical prediction", J. Am. Chem. Soc. 106, 5805-5808 (1984);
(b) B.F. Yates, W.J. Bouma and L. Radom, "Distonic radical cations: guidelines for the assessment for their stability", Tetrahedron 42, 6225-6234 (1986);
(c) S. Hammerum, "Distonic radical cations in gaseous and condensed phase", Mass Spectrom. Rev. 7, 123-202 (1988);
(d) G. Bouchoux, "Keto-enol tautomers and distonic ions - The chemistry of [CNH2NO] radical cations", Mass Spectrom. Rev. 7, 203-255 (1988).
See, for instance: (a) K.M. Stirk, J.C. Orlowski, D.T. Leeck and H.I. Kenttämaa, "The identification of distonic radical cations on the basis of a reaction with dimethyl disulfide", J. Am. Chem. Soc. 114, 8604-8606 (1992); (b) K.G. Stirk and H.I. Kenttämaa, "Radical type reactivity in a γ-distonic radical cation: a gas-phase experimental study", J. Am. Chem. Soc. 113, 5880-5881 (1991); (c) E.D. Nelson, A. Artau, J.P. Price, S.E. Tichy and H.I. Kenttämaa, "m-Benzyne reacts as an electrophile", J. Am. Chem. Soc. 122, 8781-8782 (2000); (d) K.K. Thoen and H.I. Kenttämaa, "Reactivity of a substituted m-benzyne biradical", J. Am. Chem. Soc. 121, 800-805 (1999) and references cited therein.
See, for instance: (a) K.M. Stirk, J.C. Orlowski, D.T. Leeck and H.I. Kenttämaa, "The identification of distonic radical cations on the basis of a reaction with dimethyl disulfide", J. Am. Chem. Soc. 114, 8604-8606 (1992); (b) K.G. Stirk and H.I. Kenttämaa, "Radical type reactivity in a γ-distonic radical cation: a gas-phase experimental study", J. Am. Chem. Soc. 113, 5880-5881 (1991); (c) E.D. Nelson, A. Artau, J.P. Price, S.E. Tichy and H.I. Kenttämaa, "m-Benzyne reacts as an electrophile", J. Am. Chem. Soc. 122, 8781-8782 (2000); (d) K.K. Thoen and H.I. Kenttämaa, "Reactivity of a substituted m-benzyne biradical", J. Am. Chem. Soc. 121, 800-805 (1999) and references cited therein.
See, for instance: (a) K.M. Stirk, J.C. Orlowski, D.T. Leeck and H.I. Kenttämaa, "The identification of distonic radical cations on the basis of a reaction with dimethyl disulfide", J. Am. Chem. Soc. 114, 8604-8606 (1992); (b) K.G. Stirk and H.I. Kenttämaa, "Radical type reactivity in a γ-distonic radical cation: a gas-phase experimental study", J. Am. Chem. Soc. 113, 5880-5881 (1991); (c) E.D. Nelson, A. Artau, J.P. Price, S.E. Tichy and H.I. Kenttämaa, "m-Benzyne reacts as an electrophile", J. Am. Chem. Soc. 122, 8781-8782 (2000); (d) K.K. Thoen and H.I. Kenttämaa, "Reactivity of a substituted m-benzyne biradical", J. Am. Chem. Soc. 121, 800-805 (1999) and references cited therein.
See, for instance: (a) K.M. Stirk, J.C. Orlowski, D.T. Leeck and H.I. Kenttämaa, "The identification of distonic radical cations on the basis of a reaction with dimethyl disulfide", J. Am. Chem. Soc. 114, 8604-8606 (1992); (b) K.G. Stirk and H.I. Kenttämaa, "Radical type reactivity in a γ-distonic radical cation: a gas-phase experimental study", J. Am. Chem. Soc. 113, 5880-5881 (1991); (c) E.D. Nelson, A. Artau, J.P. Price, S.E. Tichy and H.I. Kenttämaa, "m-Benzyne reacts as an electrophile", J. Am. Chem. Soc. 122, 8781-8782 (2000); (d) K.K. Thoen and H.I. Kenttämaa, "Reactivity of a substituted m-benzyne biradical", J. Am. Chem. Soc. 121, 800-805 (1999) and references cited therein.
See, for instance: (a) P. Gerbaux, Y. Van Haverbeke and R. Flammang, "Ion-molecule reaction of pyridine with CS3 radical cations: experimental evidence for the production of pyridine N-thioxide distonic ions", J. Mass Spectrom. 32, 1170-1178 (1997); (b) K.G. Stirk and H.I. Kenttämaa, "Bimolecular reactions of the β-distonic isomer of the ethanol radical cation: •CH2CH2OH 2+", J. Phys. Chem. 96, 5272-5276 (1992); (c) S.J. Yu, M.L. Gross and K.R. Fountain, "CH2•+ Transfer to pyridine nucleophiles: a means of producing α-distonic ions", J. Am. Soc. Mass Spectrom. 4, 117-124 (1993); (d) E.D. Nelson, R. Li and H.I. Kenttämaa, "Reactions of tert-butyl isocyanide with distonic radical cations", Int. J. Mass Spectrom. 185-187, 91-96 (1999); and references cited therein.
See, for instance: (a) P. Gerbaux, Y. Van Haverbeke and R. Flammang, "Ion-molecule reaction of pyridine with CS3 radical cations: experimental evidence for the production of pyridine N-thioxide distonic ions", J. Mass Spectrom. 32, 1170-1178 (1997); (b) K.G. Stirk and H.I. Kenttämaa, "Bimolecular reactions of the β-distonic isomer of the ethanol radical cation: •CH2CH2OH 2+", J. Phys. Chem. 96, 5272-5276 (1992); (c) S.J. Yu, M.L. Gross and K.R. Fountain, "CH2•+ Transfer to pyridine nucleophiles: a means of producing α-distonic ions", J. Am. Soc. Mass Spectrom. 4, 117-124 (1993); (d) E.D. Nelson, R. Li and H.I. Kenttämaa, "Reactions of tert-butyl isocyanide with distonic radical cations", Int. J. Mass Spectrom. 185-187, 91-96 (1999); and references cited therein.
See, for instance: (a) P. Gerbaux, Y. Van Haverbeke and R. Flammang, "Ion-molecule reaction of pyridine with CS3 radical cations: experimental evidence for the production of pyridine N-thioxide distonic ions", J. Mass Spectrom. 32, 1170-1178 (1997); (b) K.G. Stirk and H.I. Kenttämaa, "Bimolecular reactions of the β-distonic isomer of the ethanol radical cation: •CH2CH2OH 2+", J. Phys. Chem. 96, 5272-5276 (1992); (c) S.J. Yu, M.L. Gross and K.R. Fountain, "CH2•+ Transfer to pyridine nucleophiles: a means of producing α-distonic ions", J. Am. Soc. Mass Spectrom. 4, 117-124 (1993); (d) E.D. Nelson, R. Li and H.I. Kenttämaa, "Reactions of tert-butyl isocyanide with distonic radical cations", Int. J. Mass Spectrom. 185-187, 91-96 (1999); and references cited therein.
See, for instance: (a) P. Gerbaux, Y. Van Haverbeke and R. Flammang, "Ion-molecule reaction of pyridine with CS3 radical cations: experimental evidence for the production of pyridine N-thioxide distonic ions", J. Mass Spectrom. 32, 1170-1178 (1997); (b) K.G. Stirk and H.I. Kenttämaa, "Bimolecular reactions of the β-distonic isomer of the ethanol radical cation: •CH2CH2OH 2+", J. Phys. Chem. 96, 5272-5276 (1992); (c) S.J. Yu, M.L. Gross and K.R. Fountain, "CH2•+ Transfer to pyridine nucleophiles: a means of producing α-distonic ions", J. Am. Soc. Mass Spectrom. 4, 117-124 (1993); (d) E.D. Nelson, R. Li and H.I. Kenttämaa, "Reactions of tert-butyl isocyanide with distonic radical cations", Int. J. Mass Spectrom. 185-187, 91-96 (1999); and references cited therein.
See, for instance: (a) L.A.B. Moraes and M.N. Eberlin, "Acyclic distonic acylium ions: dual free radical and acylium ion reactivity in a single molecule", J. Am. Soc. Mass Spectrom. 11, 697-704 (2000); (b) T. Weiske, H. van der Wel, N.M.M. Nibbering and H. Schwarz, "Reactivity of CH 2-X-CH3•+ (X=Cl, Br) with electrophiles and nucleophiles in the gas phase, a Fourier Transform Resonance investigation", Ang. Chem., Int. Ed. Engl. 96, 694-699 (1984) and references cited therein.
See, for instance: (a) L.A.B. Moraes and M.N. Eberlin, "Acyclic distonic acylium ions: dual free radical and acylium ion reactivity in a single molecule", J. Am. Soc. Mass Spectrom. 11, 697-704 (2000); (b) T. Weiske, H. van der Wel, N.M.M. Nibbering and H. Schwarz, "Reactivity of CH 2-X-CH3•+ (X=Cl, Br) with electrophiles and nucleophiles in the gas phase, a Fourier Transform Resonance investigation", Ang. Chem., Int. Ed. Engl. 96, 694-699 (1984) and references cited therein.
(a) M.N. Eberlin, A.E.P.M. Sorrilha, F.C. Gozzo and R.S. Pimpim, "Novel [3+2] 1,3-cycloaddition of the ionized carbonyl ylide +CH2OCH2• with carbonyl compounds in the gas phase", J. Am. Chem. Soc. 119, 3550-3557 (1997);
(b) P. Gerbaux, M. Barbieux-Flammang, R. Flammang and G. Bouchoux, "Ion-molecule reactions between ionized nitrile oxides and neutral nitriles", Int. J. Mass Spectrom. 219, 643-658 (2002).
(a) K.M. Stirk, R.L. Smith, J.C. Orlowski and H.I. Kenttämaa, "Bimolecular reactions involving the radical site of the distonic ion •CH2CH2CH2C+O", Rapid Commun. Mass Spectrom. 7, 392-399 (1993);
(b) R.L. Smith, K.K. Thoen, K.M. Stirk and H.I. Kenttämaa, "Reactions of alkyl halides with distonic acylium radical cations", Int. J. Mass Spectrom. Ion Processes 165/166, 315-325 (1997).
(a) R.L. Smith, L.J. Chyall, K.M. Stirk and H.I. Kenttämaa, "Reaction-type reactivity of the methylenedimethylsulfonium ion, (CH 3)2S+-CH2•", Org. Mass Spectrom. 28, 1623-1631 (1993);
(b) J.L. Heidbrink, K.K. Thoen and H.I. Kenttämaa, "Polar effects on iodine atom abstraction by charged phenyl radicals", J. Org. Chem. 65, 645-651 (2000) and references cited therein.
P. Gerbaux, Y. Van Haverbeke and R. Flammang, "Experimental and theoretical study of the gas-phase interaction between ionized nitrile sulfides and pyridine", J. Am. Soc. Mass Spectrom. 14, 241-252 (2003).
(a) R.H. Bateman, J. Brown, M. Lefevere, R. Flammang and Y. Van Haverbeke, "Applications in gaseous ion and neutral chemistry using a 6-sector mass spectrometer", Int. J. Mass. Spectrom. Ion Processes 115, 205-218 (1992);
(b) R. Flammang, Y. Van Haverbeke, C. Braybrook and J. Brown, "A new hybrid mass spectrometer for the investigation of ion/molecule reactions", Rapid Commun. Mass Spectrom. 9, 795-799 (1995).
M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuserai, M.A. Robb, J.R. Cheeseman, V.G. Zakrzewski, J.A. Montgomery, R.E. Stratmann, J.C. Burant, S. Dapprich, J.M. Millam, A.D. Daniels, K.N. Kudin, M.C. Strain, O. Farkas, J. Tomasi, V. Barone, M. Cossi, R. Cammi, B. Mennucci, C. Pomelli, C. Adamo, S. Clifford, J. Ochterski, G.A. Petersson, P.Y. Ayala, Q. Cui, K. Morokuma, D.K. Malick, A.D. Rabuck, K. Raghavachari, J.B. Foresman, J. Cioslowski, J.V. Ortiz, B.B. Stefanov, B.B. Liu, A. Liashenko, P. Piskorz, A. Komaromi, R. Gomperts, R.L. Martin, D.J. Fox, T. Keith, M.A. Al-Laham, C.Y. Peng, M.W. Nanayakkara, C. Gonzalez, M. Challacombe, P.M.W. Gill, B.G. Johnson, W. Chen, M.W. Wong, J.L. Andres, M. Head-Gordon, E.S. Reploge and J.A. Pople, Gaussian 98. Gaussian, Inc., Pittsburg, PA (1998).
(a) H.B. Schlegel, "Potential energy curves using unrestricted Møller-Plesset perturbation theory with spin annihilation", J. Chem. Phys. 84, 4530-4532 (1986);
(b) I. Mayer, "The spin-projected extended Hartree-Fock method", Adv. Quantum Chem. 12, 189-196 (1980).
M. Polasek and F. Tureček, "Hydrogen atom adducts to nitrobenzene: formation of the phenylnitronic radical in the gas phase and energetics of Wheland intermediates", J. Am. Chem. Soc. 122, 9511-9524 (2000).
V.A. Rassolov, M.A. Ratner and J.A. Pople, "Electron correlation in chemical bonds", J. Chem. Phys. 112, 4014-4019 (2000).
(a) C. Das and M.L. Gross, "Structures of decomposing and non-decomposing gas-phase [C4H6O]•+ radical cations, -and their [C2H2O]•+ and [C3H6]•+ product ions", Org. Mass Spectrom. 25, 24-32 (1990);
(b) M.L. McKnee, P.M. Mayer and L. Radom, "An ab initio study of ionized cyclobutanone and cyclopentanone. Comparison of the thermodynamics and kinetic stabilities of the distonic isomers •CH 2(CH2)n C+=O", Eur. Mass Spectrom. 4, 23-30 (1998).
J.C. Traeger, C.E. Hudson and D.J. McAdoo, "The distonic ion •CH2CH2C+=O and its formation from ionized cyclopentanone", Org. Mass Spectrom. 24, 230-234 (1989).
C.G. De Koster, J.J. van Houte and J.J. van Thuijl, "Gas phase substitution reactions by radical cations: I. Reaction of the C - C ring-opened oxirane radical cation with pyridine", Int. J. Mass. Spectrom. Ion Processes 98, 235-245 (1990).
A.E.P.M. Sorrilha, F.C. Gozzo, R.S. Pimpim and M.N. Eberlin, "Multiple stage pentaquadrupole mass spectrometry and characterization of gas-phase ionic species. The case of the PyC2H5 •+ isomers", J. Am. Soc. Mass Spectrom. 7, 1126-1137 (1996).
M.C. Carvalho, V.F. Juliano, C. Kascheres and M.N. Eberlin, "Gas phase chemistry of the heterocumulene cations O=C=N+=C=O and O=C=C=N+=O", J. Chem. Soc., Perkin Trans. 2 2347-2352 (1997).
S.G. Lias, J.E. Bartmess, J.F. Liebman, J.L. Holmes, R.D. Levin and W.G. Mallard, "Gas-phase ion and neutral thermochemistry", J. Phys. Chem., Ref. Data 17 (1988).
G. Stork and P.M. Sher, "Regiospecific trapping of radicals from cyclization reactions. Cyclic nitrites via isocyanide trapping", J. Am. Chem. Soc. 105, 6765-6766 (1983).
B. Giese, Radicals in Organic Synthesis: formation of carbon-carbon bonds. Pergamon Press, Oxford, p. 221 (1986).
T. Drewello, N. Heinrich, W.P.M. Maas, N.M.M. Nibbering, T. Weiske and H. Schwarz, "Generation of the distonic ion CH2NH3 •+: nucleophilic substitution of the ketene cation radical by ammonia and unimolecular decarbonylation of ionized acetamide", J. Am. Chem. Soc. 109, 4810-4818 (1987).
J.C. Schwartz, A.P. Wade, C.G. Enke and R.G. Cooks, "Systematic delineation of scan modes in multidimensional mass spectrometry", Anal. Chem. 62, 1809-1818 (1990).
