Origin of the SN2 Benzylic Effect: Contributions by π Delocalization and Field/Inductive Effects

Historically, the SN2 benzylic effect is attributed to a conjugative stabilization between the phenyl ring and the reaction center in the transition state. However, recent papers have cast doubt on this explanation. We have therefore investigated the origin of the SN2 benzylic effect for two differe...

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Published in	European journal of organic chemistry Vol. 2012; no. 30; pp. 5991 - 6004
Main Authors	Rawlings, Robert E., McKerlie, Adam K., Bates, Daniel J., Mo, Yirong, Karty, Joel M.
Format	Journal Article
Language	English
Published	Weinheim WILEY-VCH Verlag 01.10.2012 WILEY‐VCH Verlag Wiley-VCH
Subjects	Chemistry Computational chemistry Conjugation Exact sciences and technology Gas-phase reactions Ion-molecule reactions Kinetics and mechanisms Mass spectrometry Noncondensed benzenic compounds Nucleophilic substitution Organic chemistry Preparations and properties Reactivity and mechanisms Substituent effects Substituent effect Ion molecule reaction Reaction center Stabilization Inductive effect Theoretical study Substituent effects Molecular interaction SN2 mechanism Electron delocalization Fluorides Energy barrier Gas-phase reactions Computational chemistry Benzylic compound Chlorides Transition state Ion-molecule reactions Heat of reaction Gas phase Conjugation Conjugated compound Nucleophilic substitution
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Abstract	Historically, the SN2 benzylic effect is attributed to a conjugative stabilization between the phenyl ring and the reaction center in the transition state. However, recent papers have cast doubt on this explanation. We have therefore investigated the origin of the SN2 benzylic effect for two different gas‐phase SN2 reactions, F– + C6H5CH2F and Cl– + C6H5CH2Cl, by carrying out two separate computational methodologies on each system – a vinylogue extrapolation (VE) methodology and a block‐localized wavefunction (BLW) methodology. The contributions we examined were (1) delocalization involving the ring's π system, and (2) field/inductive effects of the ring. For the fluoride and chloride reactions, the VE methodology suggests that delocalization contributes to a lowering of the reaction's energy barrier by 3.1 and 1.7 kcal/mol, respectively, and the BLW calculations suggest that delocalization contributes to lowering the barrier by 3.65 and 5.47 kcal/mol, respectively. Both methodologies therefore agree that π delocalization is a significant contributor to the benzylic effect. Furthermore, the VE methodology indicates that field/inductive effects also contribute to lowering the barriers by 2.2 and 3.2 kcal/mol, suggesting that a separate repulsive interaction serves to increase the barrier by 1.5 and 3.3 kcal/mol, respectively. Recent publications have called into doubt π conjugation as the origin of the SN2 benzylic effect. In this computational study, we show that π conjugation does indeed have a significant contribution to the lowering of the gas‐phase SN2 energy barrier, as does a field/inductive effect by the phenyl ring.
AbstractList	Historically, the SN2 benzylic effect is attributed to a conjugative stabilization between the phenyl ring and the reaction center in the transition state. However, recent papers have cast doubt on this explanation. We have therefore investigated the origin of the SN2 benzylic effect for two different gas‐phase SN2 reactions, F– + C6H5CH2F and Cl– + C6H5CH2Cl, by carrying out two separate computational methodologies on each system – a vinylogue extrapolation (VE) methodology and a block‐localized wavefunction (BLW) methodology. The contributions we examined were (1) delocalization involving the ring's π system, and (2) field/inductive effects of the ring. For the fluoride and chloride reactions, the VE methodology suggests that delocalization contributes to a lowering of the reaction's energy barrier by 3.1 and 1.7 kcal/mol, respectively, and the BLW calculations suggest that delocalization contributes to lowering the barrier by 3.65 and 5.47 kcal/mol, respectively. Both methodologies therefore agree that π delocalization is a significant contributor to the benzylic effect. Furthermore, the VE methodology indicates that field/inductive effects also contribute to lowering the barriers by 2.2 and 3.2 kcal/mol, suggesting that a separate repulsive interaction serves to increase the barrier by 1.5 and 3.3 kcal/mol, respectively. Recent publications have called into doubt π conjugation as the origin of the SN2 benzylic effect. In this computational study, we show that π conjugation does indeed have a significant contribution to the lowering of the gas‐phase SN2 energy barrier, as does a field/inductive effect by the phenyl ring.
Author	Rawlings, Robert E. Bates, Daniel J. Karty, Joel M. McKerlie, Adam K. Mo, Yirong
Author_xml	– sequence: 1 givenname: Robert E. surname: Rawlings fullname: Rawlings, Robert E. organization: Department of Chemistry, Elon University, Elon, NC 27244, USA, Fax: +1-336-278-6258, http://facstaff.elon.edu/jkarty – sequence: 2 givenname: Adam K. surname: McKerlie fullname: McKerlie, Adam K. organization: Department of Chemistry, Elon University, Elon, NC 27244, USA, Fax: +1-336-278-6258, http://facstaff.elon.edu/jkarty – sequence: 3 givenname: Daniel J. surname: Bates fullname: Bates, Daniel J. organization: Department of Chemistry, Elon University, Elon, NC 27244, USA, Fax: +1-336-278-6258, http://facstaff.elon.edu/jkarty – sequence: 4 givenname: Yirong surname: Mo fullname: Mo, Yirong organization: Department of Chemistry, Western Michigan University, Kalamazoo, MI 49008, USA – sequence: 5 givenname: Joel M. surname: Karty fullname: Karty, Joel M. email: jkarty@elon.edu organization: Department of Chemistry, Elon University, Elon, NC 27244, USA, Fax: +1-336-278-6258, http://facstaff.elon.edu/jkarty
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Keywords	Substituent effect Ion molecule reaction Reaction center Stabilization Inductive effect Theoretical study Substituent effects Molecular interaction SN2 mechanism Electron delocalization Fluorides Energy barrier Gas-phase reactions Computational chemistry Benzylic compound Chlorides Transition state Ion-molecule reactions Heat of reaction Gas phase Conjugation Conjugated compound Nucleophilic substitution
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References_xml	– reference: D. L. Cooper (Ed.), Valence Bond Theory, Elsevier, Amsterdam, 2002 . – reference: E. Gianinetti , M. Raimondi , E. Tornaghi , Int. J. Quantum Chem. 1996 , 60 , 157 . – reference: Y. Mo , S. D. Peyerimhoff , J. Chem. Phys. 1998 , 109 , 1687 . – reference: J. B. Barbour , J. M. Karty , J. Org. Chem. 2004 , 69 , 648 . – reference: L. M. Stock , J. Chem. Educ. 1972 , 49 , 400 -404 . – reference: A. Streitwieser , E. G. Jayasree , S. S.-H. Leung, G. S.-C. Choy, J. Org. Chem. 2005 , 70 , 8486 -8491 . – reference: S. S. Shaik , P. C. Hiberty , A Chemist's Guide to Valence Bond Theory, Wiley-Interscience, New York, 2007 . – reference: Y. Mo , P. v. R. Schleyer, Chem. Eur. J. 2006 , 12 , 2009 . – reference: K. Tanaka , G. I. Mackay , J. D. Payzant , K. Bohme , Can. J. Chem. 1976 , 54 , 1643 . – reference: D. Lauvergnat , P. C. Hiberty , J. Am. Chem. Soc. 1997 , 119 , 9478 . – reference: P. E. Peterson , C. Casey , Tetrahedron Lett. 1963 , 4 , 1569 -1572 . – reference: G. E. Branch , M. Calvin , The Theory of Organic Chemistry, Prentice Hall, New York, 1941 . – reference: J. F. King , G. T. Y. Tsang , J. Chem. Soc., Chem. Commun. 1979 , 1131 -1132 . – reference: C. H. DePuy , S. Gronert , A. Mullin , V. M. Bierbaum , J. Am. Chem. Soc. 1990 , 112 , 8650 . – reference: J. I. Lynas , C. J. M. Stirling , J. Chem. Soc., Chem. Commun. 1984 , 483 . – reference: B. Galabov , V. Nikolova , J. J. Wilke , H. F. Schaefer III , W. Allen , J. Am. Chem. Soc. 2008 , 130 , 9887 -9896 . – reference: P. C. Hiberty , C. Megret , L. Song , W. Wu , S. Shaik , J. Am. Chem. Soc. 2006 , 128 , 2836 . – reference: R. Z. Khaliullin , E. A. Cobar , R. C. Lochan , A. T. Bell , M. Head-Gordon , J. Phys. Chem. A 2007 , 111 , 8753 -8765 . – reference: R. Z. Khaliullin , M. Head-Gordon , A. T. Bell , J. Chem. Phys. 2006 , 124 , 204105 . – reference: G. Bianchi , O. W. Howarth , C. J. Samuel , G. Vlahov , J. Chem. Soc. Perkin Trans. 2 1995 , 7 , 1427 -1432 . – reference: M. J. Pellerite , J. I. Brauman , J. Am. Chem. Soc. 1983 , 105 , 2672 . – reference: C. C. Han , J. A. Dodd , J. I. Brauman , J. Phys. Chem. 1986 , 90 , 471 . – reference: A. Streitwieser , Solvolytic displacement reactions, McGraw-Hill, New York, 1962 . – reference: H. Stoll , G. Wagenblast , H. Preuss , Theor. Chim. Acta 1980 , 57 , 169 . – reference: L. C. Pauling , The Nature of the Chemical Bond, 3rd ed., Cornell University Press, Ithaca, NY, 1960 . – reference: M. J. S. Dewar , R. C. Dougherty , The PMO Theory of Organic Chemistry, Plenum Press, New York, 1975 . – reference: Y. Mo , W. Wu , Q. Zhang , J. Phys. Chem. 1994 , 98 , 10048 . – reference: E. L. Mehler , J. Chem. Phys. 1981 , 74 , 6298 . – reference: P. C. Hiberty , C. P. Byrman , J. Am. Chem. Soc. 1995 , 117 , 9870 . – reference: Y. Mo , P. C. Hiberty , P. v. R. Schleyer, Theor. Chem. Acc. 2010 , 127 , 27 -38 . – reference: W. Wu , P. Su , S. S. Shaik , P. C. Hiberty , Chem. Rev. 2011 , 111 , 7557 . – reference: Y. Mo , J. Phys. Chem. A 2009 , 113 , 5163 -5169 . – reference: S. F. Boys , F. Bernardi , Mol. Phys. 1970 , 19 , 553 -566 . – reference: O. J. Sovers , C. W. Kern , R. M. Pitzer , M. Karplus , J. Chem. Phys. 1968 , 49 , 2592 . – reference: Y. Mo , P. v. R. Schleyer, W. Wu , M. Lin , Q. Zhang , J. Gao , J. Phys. Chem. A 2003 , 107 , 10011 . – reference: R. S. Mulliken , R. G. Parr , J. Chem. Phys. 1951 , 19 , 1271 . – reference: J. C. McGowan , Nature 1947 , 159 , 644 . – reference: A. Slator , D. F. Twiss , J. Chem. Soc. 1909 , 95 , 93 . – reference: L. Song , Y. Mo , Q. Zhang , W. Wu , J. Comput. Chem. 2005 , 26 , 514 . – reference: D. L. Cooper , J. Gerratt , M. Raimondi , Nature 1986 , 323 , 699 . – reference: A. Dworkin , R. Naumann , C. Seigfred , J. Org. Chem. 2005 , 70 , 7605 . – reference: F. Dijkstra , J. H. van Lenthe , J. Chem. Phys. 2000 , 113. – reference: J. B. Conant , W. R. Kirner , J. Am. Chem. 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Snippet	Historically, the SN2 benzylic effect is attributed to a conjugative stabilization between the phenyl ring and the reaction center in the transition state....
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SubjectTerms	Chemistry Computational chemistry Conjugation Exact sciences and technology Gas-phase reactions Ion-molecule reactions Kinetics and mechanisms Mass spectrometry Noncondensed benzenic compounds Nucleophilic substitution Organic chemistry Preparations and properties Reactivity and mechanisms Substituent effects
Title	Origin of the SN2 Benzylic Effect: Contributions by π Delocalization and Field/Inductive Effects
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