Concomitant hydride and proton transfer: an essay on competing and consecutive key reactions occurring in gaseous ion/neutral complexes

Kuck D (2012)
European Journal of Mass Spectrometry 18(2): 161-181.

Zeitschriftenaufsatz | Veröffentlicht | Englisch
 
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Abstract / Bemerkung
The interplay of proton transfer and hydride transfer reactions in alkylbenzenium ions and related protonated di- and oligophenylalkanes is presented and discussed. While intra- and inter-annular proton exchange has been recognised to be a ubiquitous feature in protonated arenes, hydride abstraction is much less obvious but can become a dominating fragmentation channel in metastable ions of tert-butyl-substituted alkylbenzenium ions and related carbocations. In such cases, proton-induced release of the tert-butyl cation gives rise to ion/neutral complexes as reactive intermediates, for example, [(CH3)(3)C+center dot center dot center dot arylCH(2)(alpha)(CH2)(n) CH(2)(omega)aryl'] with n >= 0 and highly regioselective intra-complex hydride transfer occurs from all of the benzylic methylene hydride ion donor groups (alpha-CH2 and (omega)-CH2) to the tert-butyl cation acting as a Lewis acid. Substituent effects on the individual contributions to the overall hydride transfer from different donor sites, including ortho-methyl groups, in particular, and the concomitant intra-complex proton transfer from the tert-butyl cation to the neutral diarylalkane constituent corroborate the view of "bisolvated" complexes as the central intermediates, in which the carbenium ion is coordinated to both of the aromatic pi-electron systems. The role of cyclisation processes, converting the benzylic [M-H](+)-type ions into the isomeric benzenium, [M+H](+)-type ions prior to fragmentation, is demonstrated for several cases. This overall scenario, consisting of consecutive and/or competing intra-complex hydride abstraction and proton transfer, intra-annular proton shifts (H+ ring walk) and inter-annular proton transfer, hydrogen exchange ("scrambling") processes, and cyclisation and other electrophilic substitution reactions, is of general importance in this field of gas-phase ion chemistry and more recent examples concerning protonated ethers, benzylpyridinium and benzylammmonium ions are discussed in which these recurring features play central and concerted mechanistic roles as well.
Stichworte
arenium ions; benzylic cations; ammonium ions; proton; transfer; hydride transfer; cyclisation; mobile protons; ion/neutral; complexes; multi-step reactions; metastable ions; protonated arenes
Erscheinungsjahr
2012
Zeitschriftentitel
European Journal of Mass Spectrometry
Band
18
Ausgabe
2
Seite(n)
161-181
ISSN
1356-1049
Page URI
https://pub.uni-bielefeld.de/record/2518144

Zitieren

Kuck D. Concomitant hydride and proton transfer: an essay on competing and consecutive key reactions occurring in gaseous ion/neutral complexes. European Journal of Mass Spectrometry. 2012;18(2):161-181.
Kuck, D. (2012). Concomitant hydride and proton transfer: an essay on competing and consecutive key reactions occurring in gaseous ion/neutral complexes. European Journal of Mass Spectrometry, 18(2), 161-181. doi:10.1255/ejms.1171
Kuck, Dietmar. 2012. “Concomitant hydride and proton transfer: an essay on competing and consecutive key reactions occurring in gaseous ion/neutral complexes”. European Journal of Mass Spectrometry 18 (2): 161-181.
Kuck, D. (2012). Concomitant hydride and proton transfer: an essay on competing and consecutive key reactions occurring in gaseous ion/neutral complexes. European Journal of Mass Spectrometry 18, 161-181.
Kuck, D., 2012. Concomitant hydride and proton transfer: an essay on competing and consecutive key reactions occurring in gaseous ion/neutral complexes. European Journal of Mass Spectrometry, 18(2), p 161-181.
D. Kuck, “Concomitant hydride and proton transfer: an essay on competing and consecutive key reactions occurring in gaseous ion/neutral complexes”, European Journal of Mass Spectrometry, vol. 18, 2012, pp. 161-181.
Kuck, D.: Concomitant hydride and proton transfer: an essay on competing and consecutive key reactions occurring in gaseous ion/neutral complexes. European Journal of Mass Spectrometry. 18, 161-181 (2012).
Kuck, Dietmar. “Concomitant hydride and proton transfer: an essay on competing and consecutive key reactions occurring in gaseous ion/neutral complexes”. European Journal of Mass Spectrometry 18.2 (2012): 161-181.

11 Zitationen in Europe PMC

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PMID: 26383734
Elimination of benzene from protonated N-benzylindoline: benzyl cation/proton transfer or direct proton transfer?
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PMID: 23361371

84 References

Daten bereitgestellt von Europe PubMed Central.


Armentrout, 2003

Nibbering, 2005

Munson, J. Am. Chem. Soc. 88(), 1966

AUTHOR UNKNOWN, 0

Richter, Angew. Chem. Int. Ed. Engl. 17(), 1978

Cacace, Acc. Chem. Res. 21(), 1988

Audier, New. J. Chem. 13(), 1989

Mandelbaum, Mass Spectrom. Rev. 2(), 1983

Leung, Org. Mass Spectrom. 12(), 1977

Herman, Org. Mass Spectrom. 16(), 1981

Wesdemiotis, Z Naturforsch. 34(), 1979

Kuck, J. Am. Chem. Soc. 101(), 1979

Kuck, Int. J. Mass Spectrom. Ion Processes 67(), 1985

Kuck, J. Chem. Soc., Perkin Trans. 2(), 1985

Kuck, Mass Spectrom. Rev. 9(), 1990

Berthomieu, Org. Mass Spectrom. 26(), 1991

Berthomieu, Rapid Commun. Mass Spectrom. 5(), 1991

Mormann, Int. J. Mass Spectrom. 219(), 2002

Mormann, Int. J. Mass Spectrom. 267(), 2007

Kuck, Int. J. Mass Spectrom. 213(), 2002

Audier, Org. Mass Spectrom. 25(), 1990

Denhez, Rapid Commun. Mass Spectrom. 9(), 1995

Berthomieu, J. Phys. Chem. 99(), 1995

Kuck, J. Am. Chem. Soc. 114(), 1992

Matthias, Org. Mass Spectrom. 28(), 1993

Matthias, Eur. Mass Spectrom. 1(), 1995

Matthias, Int. J. Mass Spectrom. 199(), 2000

Matthias, Int. J. Mass Spectrom. 217(), 2002

Matthias, Int. J. Mass Spectrom. 255(), 2006

Matthias, Int. J. Mass Spectrom. 228(), 2003

Matthias, Croat. Chem. Acta 82(), 2009

Kuck, Int. J. Mass Spectrom. 306(), 2011

Morton, Tetrahedron 38(), 1982

McAdoo, Mass Spectrom. Rev. 7(), 1988

Bowen, Acc. Chem. Res. 24(), 1991

Morton, Org. Mass Spectrom. 27(), 1992

McAdoo, Acc. Chem. Res. 26(), 1993

Morton, 2003

Morton, 2005

Kuck, Int. J. Mass Spectrom. 306(), 2011

Kuck, Mass Spectrom. Rev. 9(), 1990

Kuck, 2005

Kuck, 2005

Kuck, 2005

Kuck, J. Label. Comp. Radiopharm. 50(), 2007

Kuck, J. Chem. Soc., Perkin Trans. 2(), 1990

Kuck, Org. Mass Spectrom. 21(), 1986

Holmes, J. Label. Comp. Radiopharm. 50(), 2007

Kuck, Int. J. Mass Spectrom. 179(), 1998

Kuck, Int. J. Mass Spectrom. 179(), 1998

Kuck, Int. J. Mass Spectrom. Ion Processes 117(), 1992

Sürig, Org. Mass Spectrom. 28(), 1993

Shannon, Aust. J. Chem. 15(), 1962
Even-electron ions: a systematic study of the neutral species lost in the dissociation of quasi-molecular ions.
Levsen K, Schiebel HM, Terlouw JK, Jobst KJ, Elend M, Preiss A, Thiele H, Ingendoh A., J Mass Spectrom 42(8), 2007
PMID: 17605143

Filges, Org. Mass Spectrom. 21(), 1986

Filges, Org. Mass Spectrom. 22(), 1987

Grützmacher, Int. J. Mass Spectrom. Ion Processes 98(), 1990

Filges, Int. J. Mass Spectrom. Ion Processes 83(), 1988

Grützmacher, Int. J. Mass Spectrom. Ion Processes 118(), 1992

Maksić, 1998
The critical evaluation of a comprehensive mass spectral library.
Ausloos P, Clifton CL, Lias SG, Mikaya AI, Stein SE, Tchekhovskoi DV, Sparkman OD, Zaikin V, Zhu D., J. Am. Soc. Mass Spectrom. 10(4), 1999
PMID: 10197350
Unknown identification using reference mass spectra. Quality evaluation of databases.
McLafferty FW, Stauffer DA, Loh SY, Wesdemiotis C., J. Am. Soc. Mass Spectrom. 10(12), 1999
PMID: 10584326
Mobile and localized protons: a framework for understanding peptide dissociation.
Wysocki VH, Tsaprailis G, Smith LL, Breci LA., J Mass Spectrom 35(12), 2000
PMID: 11180630
Do isopropyl and tert-butyl cations form pi complexes with benzene?
Heidrich D., Angew. Chem. Int. Ed. Engl. 41(17), 2002
PMID: 12207391
A computational study of tert-butylbenzenium ions.
Kolboe S., J Phys Chem A 115(14), 2011
PMID: 21428316
Computational study of isopropylbenzenium ions.
Kolboe S., J Phys Chem A 116(14), 2012
PMID: 22413902

Sen, Can. J. Chem. 60(), 1982

Linstrom, 0

Crestoni, J. Phys. Chem. 99(), 1995

Crestoni, J. Phys. Chem. 99(), 1995

Chiavarino, Int. J. Mass Spectrom. Ion Processes 148(), 1995

Crestoni, Chem. Eur. J. 4(), 1998

Fornarini, Acc. Chem. Res. 31(), 1998
Complexes between lithium cation and diphenylalkanes in the gas phase: the pincer effect.
Gal JF, Maria PC, Mo O, Yanez M, Kuck D., Chemistry 12(29), 2006
PMID: 16927258

Katritzky, J. Am. Chem. Soc. 112(), 1990

Katritzky, J. Am. Chem. Soc. 112(), 1990

Derwa, Org. Mass Spectrom. 26(), 1991
Fragmentation of benzylpyridinium "thermometer" ions and its effect on the accuracy of internal energy calibration.
Barylyuk KV, Chingin K, Balabin RM, Zenobi R., J. Am. Soc. Mass Spectrom. 21(1), 2009
PMID: 19879774

Cameron, J. Am. Chem. Soc. 101(), 1979

Grützmacher, Int. J. Mass Spectrom. 179(), 1998
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