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Free Energy Relationships for Reactions of Substituted Benzhydrylium Ions: From Enthalpy over Entropy to Diffusion Control

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Department Chemie, Ludwig-Maximilians-Universität München, Butenandtstrasse 5-13 (Haus F), 81377 München, Germany
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Cite this: J. Am. Chem. Soc. 2012, 134, 33, 13902–13911
Publication Date (Web):July 27, 2012
https://doi.org/10.1021/ja306522b
Copyright © 2012 American Chemical Society
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    Abstract

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    Second-order rate constants k2 for the reactions of various donor- and acceptor-substituted benzhydrylium ions Ar2CH+ with π-nucleophiles in CH2Cl2 were determined by laser flash irradiation of benzhydryl triarylphosphonium salts Ar2CH-PAr3+X– in the presence of a large excess of the nucleophiles. This method allowed us to investigate fast reactions up to the diffusional limit including reactions of highly reactive benzhydrylium ions with m-fluoro and p-(trifluoromethyl) substituents. The rate constants determined in this work and relevant literature data were jointly subjected to a correlation analysis to derive the electrophilicity parameters E for acceptor-substituted benzhydrylium ions, as defined by the linear free energy relationship log k2(20 °C) = sN(N + E). The new correlation analysis also leads to the N and sN parameters of 18 π-nucleophiles, which have only vaguely been characterized previously. The correlations of log k2 versus E are linear well beyond the range where the activation enthalpies ΔH⧧ of the reactions are extrapolated to reach the value of ΔH⧧ = 0, showing that the change from enthalpy control to entropy control does not cause a bend in the linear free energy relationship, a novel manifestation of the compensation effect. A flattening of the correlation lines only occurs for k2 > 108 M–1 s–1 when the diffusion limit is approached.

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    87. Feng An, Shyeni Paul, Johannes Ammer, Armin R. Ofial, Peter Mayer, Sami Lakhdar, Herbert Mayr. Structures and Reactivities of Iminium Ions Derived from Substituted Cinnamaldehydes and Various Chiral Imidazolidin‐4‐ones. Asian Journal of Organic Chemistry 2014, 3 (4) , 550-555. https://doi.org/10.1002/ajoc.201402009
    88. Hans A. Laub, Herbert Mayr. Electrophilic Alkylations of Vinylsilanes: A Comparison of α- and β-Silyl Effects. Chemistry - A European Journal 2014, 20 (4) , 1103-1110. https://doi.org/10.1002/chem.201303215
    89. Roland Wilcken, Herbert Mayr, Eberhard Riedle. Bimolecular Reactions on a Timescale below 1 ps. 2014, 07.Mon.E.5. https://doi.org/10.1364/UP.2014.07.Mon.E.5
    90. Johannes Ammer, Herbert Mayr. Photogeneration of carbocations: applications in physical organic chemistry and the design of suitable precursors. Journal of Physical Organic Chemistry 2013, 26 (12) , 956-969. https://doi.org/10.1002/poc.3132
    91. Biplab Maji, Konstantin Troshin, Herbert Mayr. Ambidente Reaktivität von Formaldehyd- N , N -dialkylhydrazonen. Angewandte Chemie 2013, 125 (45) , 12116-12120. https://doi.org/10.1002/ange.201305092
    92. Biplab Maji, Konstantin Troshin, Herbert Mayr. Ambident Reactivities of Formaldehyde N , N -Dialkylhydrazones. Angewandte Chemie International Edition 2013, 52 (45) , 11900-11904. https://doi.org/10.1002/anie.201305092
    93. Nobutaka Yamaoka, Kohei Sumida, Itsuki Itani, Hiroko Kubo, Yusuke Ohnishi, Sho Sekiguchi, Toshifumi Dohi, Yasuyuki Kita. Single-Electron-Transfer (SET)-Induced Oxidative Biaryl Coupling by Polyalkoxybenzene-Derived Diaryliodonium(III) Salts. Chemistry - A European Journal 2013, 19 (44) , 15004-15011. https://doi.org/10.1002/chem.201301148
    94. Johannes Ammer, Christoph Nolte, Konstantin Karaghiosoff, Sebastian Thallmair, Peter Mayer, Regina de Vivie-Riedle, Herbert Mayr. Ion-Pairing of Phosphonium Salts in Solution: CH⋅⋅⋅Halogen and CH⋅⋅⋅π Hydrogen Bonds. Chemistry - A European Journal 2013, 19 (43) , 14612-14630. https://doi.org/10.1002/chem.201204561
    95. Florian Kniep, Stefan H. Jungbauer, Qi Zhang, Sebastian M. Walter, Severin Schindler, Ingo Schnapperelle, Eberhardt Herdtweck, Stefan M. Huber. Organokatalyse mit neutralen mehrzähnigen Halogenbrückendonoren. Angewandte Chemie 2013, 125 (27) , 7166-7170. https://doi.org/10.1002/ange.201301351
    96. Florian Kniep, Stefan H. Jungbauer, Qi Zhang, Sebastian M. Walter, Severin Schindler, Ingo Schnapperelle, Eberhardt Herdtweck, Stefan M. Huber. Organocatalysis by Neutral Multidentate Halogen-Bond Donors. Angewandte Chemie International Edition 2013, 52 (27) , 7028-7032. https://doi.org/10.1002/anie.201301351
    97. Biplab Maji, Mahiuddin Baidya, Johannes Ammer, Shinjiro Kobayashi, Peter Mayer, Armin R. Ofial, Herbert Mayr. Nucleophilic Reactivities and Lewis Basicities of 2-Imidazolines and Related N-Heterocyclic Compounds. European Journal of Organic Chemistry 2013, 2013 (16) , 3369-3377. https://doi.org/10.1002/ejoc.201300213
    98. Christian F. Sailer, Sebastian Thallmair, Benjamin P. Fingerhut, Christoph Nolte, Johannes Ammer, Herbert Mayr, Igor Pugliesi, Regina de Vivie‐Riedle, Eberhard Riedle. A Comprehensive Microscopic Picture of the Benzhydryl Radical and Cation Photogeneration and Interconversion through Electron Transfer. ChemPhysChem 2013, 14 (7) , 1423-1437. https://doi.org/10.1002/cphc.201201057
    99. Markus Horn, Ludwig H. Schappele, Gabriele Lang-Wittkowski, Herbert Mayr, Armin R. Ofial. Towards a Comprehensive Hydride Donor Ability Scale. Chemistry - A European Journal 2013, 19 (1) , 249-263. https://doi.org/10.1002/chem.201202839
    100. Johannes Ammer, Herbert Mayr. Solvent nucleophilicities of hexafluoroisopropanol/water mixtures. Journal of Physical Organic Chemistry 2013, 26 (1) , 59-63. https://doi.org/10.1002/poc.3064
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